Dioxane derivatives

ABSTRACT

Dioxane derivatives for use as components in liquid crystal devices (LCDs) of general formula (A), wherein X is CH or B; R 1 , R 2  are each A 1 , OA 1 , OCOA 2 , or COOA 2  ; A 1  is a straight or branched chain alkyl group containing from 1 to 20 carbon atoms and may be substituted with one or more F or CN. A 2  is a straight or branched chain alkyl group containing from 1 to 20 carbon atoms and may be substituted with one or more F or CN and if straight may be unsubstituted. Y 1 , Y 2 , Y 3  may each be (CH 2 ) p , (CH 2 ) p  COO or OCO(CH 2 ) p  ; p is from 0 to 10, n is 0 or 1, m is 0 or 1, either or both of Z 1  and Z 2  are F and, when not F, are H; Y 4  is a covalent bond or, when n is 0, may be (a) LCDs, containing the devices exhibit very fast switching speed, bi-stable characteristics, enhanced greyscale and storage capabilities and a wide viewing angle.

This application is a continuation of 371 application PCT GB 93/01929

This invention relates to dioxane derivatives which are useful ascomponents in liquid crystal compositions. Such compositions may beincorporated in liquid crystal devices (LCD) and exhibit usefulelectro-optical effects. The invention also relates to such compositionsand to the LCDs incorporating them. In particular it relates to thosecompositions which exhibit ferroelectric behaviour and allow the LCDscontaining them to have very fast switching speed, bi-stablecharacteristics, enhanced greyscale and storage capabilities and wideviewing angle.

Accordingly we provide a compound of the formula A: ##STR2## Wherein Xis CH or B R¹, R², are each A¹, OA¹, OCOA², or COOA²

A¹ is a straight or branched chain alkyl group containing from 5 to 10carbon atoms and may be substituted with one or more F or CN.

A² is a straight or optically active branched chain alkyl groupcontaining from 5 to 10 carbon atoms and may be substituted with one ormore F or CN and if straight may be unsubstituted.

Y², Y³ may each be (CH₂)_(p), (CH₂)_(p) COO or OCO(CH₂)_(p)

p is from 0 to 10

m is 1 or, if X is CH and Y³ and Y⁴ are covalent bonds, may be 0 eitheror both of Z₁ and Z₂ are F and, when not F, are H

Y⁴ is a covalent bond or ##STR3##

Particularly useful compounds are those wherein A² is an opticallyactive branched chain alkyl group substituted by a single F or CN.

Individual compounds which have been found to be particularly usefulinclude the following.

2-(4"-heptyl-2",3"-difluoro-biphen-4'-yl)-5-n-octyl-1,3-dioxane,(compound A),

2-(4"-hexyl-2",3"-difluoro-biphen-4'-yl)-5-n-octyl-1,3-dioxane,(compound B),

2-(4"-heptoxy-2",3"-difluoro-biphen-4'-yl)-5-n-nonyl-1,3-dioxane,(compound C),

2-(4"-octoxy-2",3"-difluoro-biphen-4'-yl)-5-n-nonyl-1,3-dioxane,(compound D),

2-(4"-octoxy-2",3"-difluoro-biphen-4'-yl)-5-n-heptyl-1,3-dioxane,(compound E),

2-(4"-octoxy-2',3'-difluoro-biphen-4'-yl)-5-n-heptyl-1,3-dioxane,(compound F),

4"-n-nonyl-2",3"-difluoro-4-(5'-n-pentyl-1',3'-dioxane-2-yl)benzoate,(compound G),

2",3"-difluoro-4"-n-nonoxy-4'-biphenyl)-4-n-nonyl-2,6-dioxaborinane(compound H)

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustration of a compound production scheme according tothe invention.

FIG. 2 is another illustration of a compound production scheme.

FIG. 3 is another illustration of a compound production scheme.

FIG. 4 is another illustration of a compound production scheme.

The compounds of this invention may be synthesised by the followingmethods.

Compounds of the formula 11 ##STR4## i.e. wherein, in general formula A,X is CH;

Y², Y³ are each (CH₂)_(p), wherein p is 0;

m is 1;

Z₁ is F and Z₂ is H.

These compounds are produced according to the scheme illustrated inFIG. 1. In this scheme diethyl malonate (formula 1) is reacted with thecompound R¹ Br in sodium ethoxide/ethanol to give the R¹ -substituteddiethyl malonate of formula 2. Reduction of this with lithium aluminiumhydride in ether yields the corresponding diol (formula 3) which is thenreacted with 4-bromobenzaldehyde and 4-toluene sulphonic acid in drytoluene to give the compound of formula 4. Reaction of1,2-difluorobenzene (formula 5) with the compound

R³ CHO where R³ is a straight or branched chain alkyl group containingfrom 1 to 18 carbon atoms, optionally substituted with one or more F orCN, with n-butyllithium in tetrahydrofuran followed by treatment withphosphorous pentoxide in light petrol and then by reduction overpalladium charcoal yields the compound of formula 6. Treatment of thiscompound with n-butyllithium in tetrahydrofuran followed by triisopropylborate gives the compound of formula 7. Finally the compounds offormulae 4 and 7 are reacted in the presence oftetrakis(triphenylphosphine) palladium and aqueous sodium carbonate toyield the required compound of formula 11.

Compounds of Formula 12 ##STR5## i.e. wherein, in general formula A, Xis CH;

Y², Y³ are each (CH₂)_(p), wherein p is 0;

m is 1;

Z₁ is F and Z₂ is H

Referring again to the scheme illustrated in FIG. 1, reaction of2,3-difluorophenol (formula 8) with the compound R2Br over potassiumcarbonate in acetone gives the 2,3-difluorophenyl compound of formula 9which on reaction with firstly butyl lithium under nitrogen at -78° C.and then with tri-isopropyl borate gives the compound of formula 10. Thecompounds of formulae 4 and 10 are then reacted in the presence oftetrakis(triphenylphosphine) palladium and aqueous sodium carbonate toyield the required compound of formula 12.

Compounds of the formula 15 ##STR6## i.e. wherein, in general formula A,X is CH;

Y² is (CH₂)_(p), wherein p is 0;

Y³ is (CH₂)_(p) COO, wherein p is 0;

m is 1;

Z₁ is F and Z₂ is H.

These compounds are produced according to the scheme illustrated in FIG.2. In this scheme, the compound of formula 4 (see FIG. 1 and descriptionabove), after reaction with n-butyllithium in THF under nitrogen, ispoured onto carbon dioxide granules giving the 4-substituted benzoicacid of formula 13. The compound of formula 7 (see also FIG. 1) isconverted to the corresponding phenol of formula 14 by reaction withhydrogen peroxide in ether. The compounds of formulae 13 and 14 are thenreacted with N,N'-dicyclophenxylcarbodiimide and 4-dimethylaminopyridineto yield the required compound of formula 15.

Compounds of the formula 19 ##STR7## i.e. wherein, in general formula A,X is B;

Y², Y³ are each (CH₂)_(p), wherein p is 0;

m is 1;

Z₁ is F and Z₂ is H

These compounds are produced according to the scheme illustrated in FIG.3. In this scheme, the compound of formula 7 (see FIG. 1) is reactedwith 4-bromoiodobenzene and tetrakis (triphenylphosphine) palladium togive the product of formula 17 which, on reaction with n-butyllithiumunder nitrogen at -78° C. and then with triisopropyl borate yields thecompound of formula 18. Finally, reaction of this with the2-substituted-1,3-propandiol of formula 3 and 4-toluene sulphonic acidin dry toluene gives the required product of formula 19.

Compounds of the formula 24 ##STR8## wherein, in the general formula A,X is CH;

Y², Y³ are each (CH₂)_(p), where p is 0;

m is 1;

Z₁ is H and Z₂ is F.

These compounds are produced according to the scheme illustrated in FIG.4. In this scheme, the compound of formula 3 (see FIG. 1) is reactedwith 2,3-difluorobenzaldehyde (formula 20) and 4-toluene sulphonic acidin dry benzene to give the compound of formula 21 which, when reactedfirst with n-butyllithium in tetrahydrofuran under nitrogen at -78° C.and then with trisopropylborate in the same solvent and under the sameconditions followed by warming and treatment with hydrochloric acidyields the compound of formula 22. Reaction of this with the compound offormula 23 wherein Q is bromine or iodine withtetrakis(triphenylphosphine) palladium gives the required compound offormula 24.

Compounds of formula 25 ##STR9## i.e. wherein, in general formula A, Xis CH;

Y³ is (CH₂)_(p) and p is 0;

m is 0;

and Y⁴ is a covalent bond.

Reaction of the compound of formula 21 (see FIG. 4) with n-butyllithiumin tetrahydrofuran under nitrogen at -78° C. with a solution of the iodocompound of formula R² I in tetrahydrofuran gives the required compoundof formula 25.

Compounds of formula 27 ##STR10##

To obtain the compounds of formula 27, the compound of formula 22 (seeFIGS. 4 and 5) is reacted first with hydrogen peroxide in ether andsodium carbonate to give the compound of formula 26 which is thenreacted with a bromo compound A¹ Br to give the required compound offormula 27.

Compounds of Formula 31 ##STR11## i.e. wherein, in general formula A: Xis CH

Y², Y³ are each (CH₂)_(p) and p is 0;

m is 1;

Z₁ is F and Z₂ is H

Reaction of compound of formula 4 with 2,3-difluorophenylboronic acidand with tetrakis-(triphenylphosphine) palladium yields the compound offormula 29 (see FIG. 6) which, on reaction with n-butyllithium andtriisopropyl borate followed by hydrogen peroxide gives the compound offormula 30. The required compound of formula 31 is obtained by reactionof the compound of formula 30 with an acid of formula A² COOH in thepresence of N,N'-dicyclohexylcarbodiimide and 4-dimethylaminopyridine.

Compounds of formula 33 ##STR12## i.e. wherein in general formula A: Xis CH

Y², Y³ are each (CH₂)_(p) and p is 0;

m is 1;

Z₁ is F and Z₂ is H.

As illustrated in FIG. 7, the compound of formula 29 (see FIG. 6) isreacted with n-butyllithium and then poured onto carbon dioxide granulesto give the benzoic acid of formula 32. Reaction of this compound withA² OH in the presence of N,N'-dicyclohexylcarbodiimide and4-dimethylaminopyridine gives the required compound of formula 33.

Compositions comprising one or more of the compounds of this inventionfor use in LCDs have been prepared and incorporated in cells for use inLCD devices and have demonstrated the following properties, either aloneor in a mixture with other suitable liquid cry compounds.

    ______________________________________                                        (a) Temperature Range of Smectic C Phase                                      Compound        Range (°)                                              ______________________________________                                        A               66-98                                                         B               61-98                                                         C                54-122                                                       D                43-110                                                       E/F (1:1 mixture)                                                                             20-67                                                         G/F (1:4 mixture)                                                                             20-82                                                         H                56-104                                                       ______________________________________                                    

(b) Other Properties

A blend of equal proportions by weight of each of the followingcompounds of formula 12 was prepared:

    ______________________________________                                               R.sup.1                                                                              A.sup.1                                                         ______________________________________                                               C.sub.5 H.sub.11                                                                     C.sub.7 H.sub.15                                                       C.sub.5 H.sub.11                                                                     C.sub.8 H.sub.17                                                       C.sub.5 H.sub.11                                                                     C.sub.9 H.sub.19                                                       C.sub.7 H.sub.15                                                                     C.sub.5 H.sub.11                                                       C.sub.7 H.sub.15                                                                     C.sub.7 H.sub.15                                                       C.sub.9 H.sub.19                                                                     C.sub.7 H.sub.15                                                       C.sub.9 H.sub.19                                                                     C.sub.9 H.sub.19                                                ______________________________________                                    

and four parts of this blend were mixed with one part of the compound offormula 11 where R¹ is C₉ H₁₉ and A¹ is C₅ H₁₁ to give Mixture 1.Mixture 1 had an Smectic C phase range from 20° C. to 97° C.

Mixture 1 was then used as an Sc host with a chiral dopant to give thefollowing mixture 2:

Mixture 1 90% by weight

chiral S-(-)-1-cyano-2-methylpropyl-4¹ -nonoxybiphenyl-4-carboxylate-1.5% by weight racemic (±)-S-(-)-1-cyano-2-methylpropyl-4¹-nonoxybiphenyl-4-carboxylate- 8.5% by weight (see Chan et al, Mol.Cryst. Liq. Cryst, 172, 125 (1989).

Mixture 2 had a Smectic C phase range from -20° C. to 93° C.

(i) Spontaneous polarisation

FIG. 9 shows the variation of spontaneous polarisation of mixture 2 withtemperature. The data was obtained using a 6 μm thick cell at 50 Hz and30 volts employing a Diamant bridge (see Rev. Sci. Instr., 28, 30(1957)).

(ii) Tilt Angle Measurements

FIG. 10 shows the variation of tilt angle, θ, with respect totemperature for mixture 2. The tilt angle was measured by applying asquare wave of 50 Hz at 30 volts to a filled 6 μm cell and the maximumand minimum transmission positions, obtained by rotating the sample,were measured using a photomultiplier, the difference between the twovalues being the cone angle, 2 θ, of the molecules in the Sc phase.

(iii) Monopolar Response Time

FIG. 11 shows the plot of response time against applied voltage. Thedata was obtained as described in Ferroelectrics, 122, 63 (1991). Amonopolar pulse of 1:100 duty cycle and alternating polarity was used toswitch the device alternately between its two optical states. Theresponse time is taken as the minimum pulse width at which visibly clearswitching occurs in the cell as observed under a crossed polarisingmicroscope.

(iv) Multiplexing Characteristic

The multiplexing characteristics for mixture 2 under real driveconditions (i.e. with random data voltage patterns) is shown in FIG. 12,using the 2-slot multiplexing scheme as described in Ferroelectrics,122, 63 (1991).

Mixture 2 exhibits a wide operating temperature range and multiplexes ataround 100 μs line address time (l.a.t.) at room temperature down to 10μs l.a.t. at 65° C.

(v) Birefringence

This is illustrated for mixture 2 in FIG. 13. The Senamont compensatortechnique was used as described in the "Nikon Polarising MicroscopeInstructions Manual", p. 34 (1990). Publisher: Nikon Inc., InstrumentGroup, 623 Stewart Avenue, Garden City, N.Y. 11530, U.S.A. As shown inFIG. 13, mixture 2 exhibited a very low birefringence of ₋₋ 0.12. Thisvalue is of the same order as the values obtained using previouslydisclosed two ring liquid crystal systems such as the phenylpyrimidinesand the biphenyls.

The liquid crystal cell comprising mixture 2, used to obtain the dataillustrated in and described with reference to FIGS. 9 to 13, may alsobe used in an electro-optical display device. The cell consists of twoglass plates, arranged parallel. On the inner surface of each plate is athin film of a transparent conducting material, e.g. indium tin oxide(ITO), coated with a transparent layer of a polymer such as Nylon 6 toprotect the conducting material and to aid surface alignment of a layerof Sc* liquid crystal material sandwiched between the coated plates. Thespace between the Nylon 6 layers defines the thickness of the layer ofthe ferroelectric liquid crystals and its edges are sealed with UVcurable glue. For the spontaneous polarisation and tilt anglemeasurements as shown in FIGS. 9 and 10 respectively, the spacing was 6μm, and for other experiments as shown in FIGS. 11 and 13, the spacingwas 1.5 μm. The cell is normally positioned between crossed polariserswhen being used in the birefringence mode referred to above.

The invention is further illustrated by the following examples to whichthe following general points apply:

General Techniques Employed

1. Chromatography Techniques

1.1 Analytical Thin-Layer Chromatography (TLC)

The TLC plates used were aluminium sheets coated with fluorescencesilica gel 60 F254 (Merck 5554, Darmstadt). The detection of spots wasachieved by UV fluorescence (254 nm) and/or by contact with iodinevapour.

1.2 Column Chromatography

Column chromatographic separations were carried out using either flashcolumn chromatography over silica gel C60-H (May & Baker, 40-60 mm) orstandard gravity column chromatography over silica gel (Fisons, 60-120mesh).

1.3 Gas-Liquid Chromatography (GLC)

The progress of many reactions and the purity of a number of productswas checked using a Perkin-Elmer 8320 capillary gas chromatographequipped with a BP1 capillary column.

1.4 High Performance Liquid Chromatography (HPLC)

The purity of all final compounds and a number of intermediates waschecked by HPLC. The system consisted of the following modules:

(i) a Kontron 420 Pump;

(ii) a Must Multi-port Stream Switch;

(iii) a Perkin-Elmer ISS-100 Auto Sampler;

(iv) a Dynamax Microsorb C18 Reverse Phase Column (25 cm);

(v) a Spectroflow 757 Absorbance Detector;

(vi) a Chessell Chart Recorder (BD 40 04);

(vii) a Perkin-Elmer 3600 Data Station.

Some products were purified by preparative HPLC.

The system consisted of the following modules:

(i) a Kontron 420 Pump (for eluent);

(a Gilson 303 Pump (for injection);

(iii) a Gilson 201-202 Controller;

(iv) a Gilson Holochrome UV Detector;

(v) a Chessell Chart Recorder (BD 40 04);

(vi) Gilson 201 Fraction Collector.

The solvent system used was methanol unless otherwise stated.

2 Assessment of Materials

2.1 Spectroscopy

(a) Infra-Red (IR) Spectroscopy

IR was carried out using a Perkin-Elmer 783 infra-red spectrophotometer.

(b) Mass Spectrometry (MS)

MS was carried out using a Finnigan-MAT 1020 automated GC/MS.

(c) Nuclear Magnetic Resonance (NMR) Spectroscopy

NMR was carried out using a JEOL JNM-GX270 FT nuclear magnetic resonancespectrometer (270 MHz).

2.2 Transition Temperatures

(a) Thermal Optical Microscopy

The transition temperatures of all mesogens were determined using anOlympus BH-2 or a Zeiss Universal polarising light microscope inconjunction with a Mettler FP52 heating stage fitted with a Mettler FP5control unit. The heating and cooling rate used was 1° min⁻¹, except foraround clearing transitions where the rate used was 0.2° min⁻¹.

(b) Differential Scanning Calorimetry (DSC)

All liquid-crystalline transitions were verified by thermal analysisusing a Perkin-Elmer DSC7 differential scanning calorimeter fitted witha TAC 7/PC instrument controller, an IBM PC/2 personal computer and aPerkin-Elmer Controlled Cooling Accessory.

A static nitrogen atmosphere was used in the furnace and the referencematerial was aluminium oxide (Al₂ O₃). Indium metal was used as thestandard for callibration purpose.

3 Drying and Purification of Solvents

(i) Benzene, diethyl ether and toluene were dried over sodium wire.

(ii) Dichloromethane was distilled over phosphorous pentoxide prior touse.

(iii) Tetrahydrofuran was distilled over sodium and benzophenone priorto use.

(iv) Pyridine was dried over anhydrous potassium hydroxide.

(v) Super-dry ethanol was distilled over magnesium turnings and iodineprior to use.

4. Abbreviations

(a) In the reporting of proton NMR data, the following abbreviationshave been used: s--single, d--doublet, t--triplet, q--quartet,qn--quintet, sex--sextet, m--multiplet.

(b) When describing mesomorphic behaviour or physical properties:

m.p.--melting point, b.p.--boiling point, K--crystalline solid,Iso--isotropic liquid phase, N--nematic phase, Sm--smectic mesophases.

(c) The solvents used:

DCC--N,N'-dicyclohexylcarbodiimide, DEAD--diethyl azodicarboxylate,DMAP--4-dimethylaminopyridine, DME--dimethoxy ethane. DMF--dimethylformamide, THF--tetrahydrofuran, TsOH--p-toluenesulfonic acidmonohydrate.

5 Nomenclature

The IUPAC system of nomenclature has been used throughout.

EXAMPLE 1

Diethyl(2-n-pentylpropanedicarboxylate) (Formula 2)

Alcoholic sodium ethoxide, prepared from sodium (7.8 g, 0.34 mol) insuper-dry ethanol (200 cm³) was cooled to ca. 50° C. and diethylmalonate (55 g, 0.34 mol) added slowly with vigorous stirring.1-Bromopentane (49.5 g, 0.33 mol) was added gradually and the mixturerefluxed until neutral to moist litmus (ca. 2 h). The solvent wasremoved in vacuo and water (200 cm³) added. The aqueous layer wasextracted with diethyl ether (2×100 cm³) and the combined ethereallayers were dried (Na₂ SO₄). The solvent was removed in vacuo and thepure product isolated by distillation under reduced pressure.

Yield=71 g (78%); b.p.=82°-87° C./0.2 mm Hg; ¹ H NMR (CDCl₃): δ0.88 (3H,t), 1.28 (12H, m), 1.88 (2H, q), 3.31 (1H, t), 4.20 (4H, q); IR: 2968,2935, 2870, 1735, 1468, 1372, 1156, 1120, 1035 cm⁻¹ ; MS: 230 M!⁺, 185,173, 160, 143.

EXAMPLE 2

Diethyl(2-n-hexylpropanedicarboxylate)

Quantities: sodium (8.1 g, 0.35 mol), diethyl malonate (57.5 g, 0.36mol) and 1-bromohexane (59.5 g, 0.36 mol). The experimental procedurewas as described in Example 1.

Yield=72.2 g (84%); b.p.=106°-110° C./0.9 mm Hg; ¹ H NMR (CDCl₃): δ0.89(3H, t), 1.28 (14H, m), 1.89 (2H, q), 3.31 (1H, t), 4.20 (4H, q); IR:2968, 2940, 2870, 1740, 1470, 1372, 1156, 1120, 1037 cm⁻¹ ; MS: 244 M!⁺,199, 173.

EXAMPLE 3

Diethyl(2-n-heptylpropanedicarboxylate)

Quantities: sodium (11.5 g, 0.5 mol), diethyl malonate (82.9 g, 0.52mol) and 1-bromoheptane (90 g, 0.5 mol). The experimental procedure wasas described in Example 1.

Yield=105 g (82%); b.p.=103°-109° C./0.3 mm Hg; ¹ H NMR (CDCl₃): δ0.90(3H,t), 1.28 (16H, t), 1.89 (2H, q), 3.32 (1H, t), 4.20 (4H, q); IR:2970, 2940, 2872, 1740, 1470, 1373, 1156, 1123, 1035 cm⁻¹ ; MS: 258 M!⁺,213, 173, 160.

EXAMPLE 4

Diethyl(2-n-octylpropanedicarboxylate)

Quantities: sodium (8.5 g, 0.37 mol), diethyl malonate (60 g, 0.37 mol)and 1-bromooctane (71.5 g, 0.37 mol). The experimental procedure was asdescribed in Example 1.

Yield=79.5 g (79%); b.p.=112°-113° C./0.3 mm Hg; ¹ H NMR (CDCl₃): δ0.88(3H, t), 1.27 (18H, t), 1.88 (2H, q), 3.31 (1H, t), 4.20 (4H, q); IR:2960, 2930, 2860, 1733, 1470, 1370, 1156, 1120, 1034 cm⁻¹ ; MS: 237, 228M-44 (CH₂ ═CHOH)!⁺, 173, 160.

EXAMPLE 5

Diethyl(2-n-nonylpropanedicarboxylate)

Quantities: sodium (11.4 g, 0.5 mol), diethylmalonate (80.5 g, 0.5 mol)and 1-bromononane (102 g, 0.49 mol). The experimental procedure was asdescribed in Example 1.

Yield=114 g (81%); b.p.=130°-138° C./1.3 mm Hg; ¹ H NMR (CDCl3): δ0.90(3H, t), 1.30 (20H, m), 1.90 (2H, q), 3.32 (1H, t), 4.20 (4H, q); IR:2965, 2935, 2865, 1740, 1472, 1374, 1156, 1035 cm⁻¹ ; MS: 287 M+1!⁺,241, 173, 160.

EXAMPLE 6

2-n-Pentylpropan-1,3-diol (Formula 3)

A solution of compound from Example 1 (59.2 g, 257 mmol) in sodium-drieddiethyl ether (50 cm3) was added dropwise to a mixture of lithiumaluminum hydride (19.5 g, 514 mmol) in dry diehtyl ether (450 cm³) withvigorous stirring and heated under gentle reflux. During this period,four 50 cm³ portions of dry diethyl ether were added. After furtherheating (1 h), water (75 cm³) was carefully added to decompose excesslithium aluminum hydride, followed by sulphuric acid (20%, 350 cm³). Theaqueous layer was extracted with diethyl ether (2×100 cm³), the combinedethereal layers washed with water (2×100 cm³) and dried (MgSO₄). Thesolvent was removed in vacuo to give the product as a colourless oil.

Yield=31 g (83%); ¹ H NMR (CDCl₃): δ0.90 (3H, t), 1.30 (8H, m), 1.77(1H, m), 2.74 (2H, s), 3.64 (2H, q), 3.82 (2H, q); IR: 3700-3040, 2962,2930, 2866, 1470, 1035 cm⁻¹ ; MS: 128 M-H₂ O!⁺, 110, 98.

EXAMPLE 7

2-n-Hexylpropan-1,3-diol

Quantities: compound from Example 2 (72.2 g, 0.3 mol) and lithiumaluminum hydride (20 g, 0.53 mol). The experimental procedure was asdescribed in Example 6. The pure product isolated by distillation underreduced pressure.

Yield=44 g (92%); b.p.=108°-110° C./0.2 mm Hg; ¹ H NMR (CDCl₃): δ0.90(3H, t), 1.30 (10H, m), 1.77 (1H, m), 2.74 (2H, s), 3.65 (2H, q), 3.82(2H, q); IR: 3700-3050, 2960, 2932, 2838, 1470, 1032 cm⁻¹ ; MS: 160 M!⁺,124, 112.

EXAMPLE 8

2-n-Heptylpropan-1,3-diol

Quantities: compound from Example 3 (72.2 g, 0.3 mol) and lithiumaluminum hydride (20 g, 0.53 mol). The experimental procedure was asdescribed in Example 6. The pure product was recrystallised from lightpetrol/ethyl acetate; (49:1).

Yield=54.5 g (77%): m.p.=32°-33° C.; ¹ H NMR (CDCl₃): δ0.90 (3H, t),1.30 (12H, m), 1.77 (1H, m), 2.55 (2H, s), 3.67 (2H, q), 3.82 (2H, q);IR: 3700-3050, 2962, 2932, 2864, 1473, 1040 cm⁻¹ ; MS: 138 M-(H₂ O)₂ !⁺,126.

EXAMPLE 9

2-n-Octylpropan-1,3-diol

Quantities: compound from Example 4 (76.5 g, 0.28 mol) and lithiumaluminum hydride (23 g, 0.6 mol). The experimental procedure was asdescribed in Example 6. The product was obtained as a colourless solid.

Yield=48.3 g (92%); ¹ H NMR (CDCl₃): δ0.88 (3H, t), 1.27 (14H, m), 1.78(1H, m), 2.60 (2H, s), 3.66 (2H, q), 3.83 (2H, q); IR: 3640-3060, 2920,2850, 1463, 1037 cm⁻¹ ; MS: 188 M!⁺, 171, 143.

EXAMPLE 10

2-n-Nonylpropan-1,3 -diol

Quantities: compound from Example 5 (76.5 g, 0.28 mol) and lithiumaluminum hydride (23 g, 0.6 mol). The experimental procedure was asdescribed in Example 6.

Yield=79 g (98%); m.p.=50.0°-50.5° C.; ¹ H NMR (CDCl₃): δ0.90 (3H, t),1.30 (16H, m), 1.78 (1H, m), 2.15 (2H, s), 3.67 (2H, q), 3.83 (2H, q);IR: 3600-3030, 2930, 2864, 1473, 1383, 1040 cm⁻¹ ; MS: 203 M+1!⁺, 202M!⁺.

EXAMPLE 11

2-(4'-Bromophenyl)-5-n-pentyl-1,3-dioxane (Formula 4)

A mixture of compound from Example 6 (31 g, 0.21 mol),4-bromobenzaldehyde (38.8 g, 0.21 mol) and 4-toluenesulphonic acid (110mg) in dry toluene (200 cm³) was heated under reflux (3 h) using a Deanand Stark apparatus. On cooling to room temperature the mixture waspoured into aqueous sodium hydrogen carbonate solution (5%, 70 cm³) andthe separated organic layer washed with aqueous sodium hydrogencarbonate solution (5%, 2×60 cm³), water (2×60 cm³) and dried (MgSO₄).The solvent was removed in vacuo and the residue purified bycrystalliation from methanol to remove the cis-isomer.

Yield=33.1 g (50%); m.p.=76.5°-77.0° C.; ¹ H NMR (CDCl₃): δ0.89 (3H, t),1.09 (2H, q), 1.29 (6H, m), 2.11 (1H, m), 3.52 (2H, t), 4.22 (2H, q),5.36 (1H, s), 7.35 (2H, m), 7.49 (2H, m); IR: 2964, 2936, 2868, 1600,1490, 1470, 1387, 1168, 1132, 1088, 1073, 1026, 1014, 982, 805 cm⁻¹ ;MS: 314 M!⁺, 312 M!⁺, 185, 183, 157, 155.

EXAMPLE 12

2-(4'-Bromophenyl)-5-n-hexyl-1,3-dioxane

Quantities: compound from Example 7 (44 g, 0.27 mol),4-bromobenzaldehyde (49 g, 0.27 mol) and 4-toluenesulphonic acid (150mg). The experimental procedure was as described in Example 11.

Yield=43.3 g (49%); m.p.=58.0°-58.5° C.; ¹ H NMR (CDCl₃): δ0.88 (3H, t),1.09 (2H, q), 1.28 (8H, m), 2.11 (1H, m), 3.52 (2H, t), 4.22 (2H, q),5.36 (1H, s), 7.36 (2H, m), , 7.49 (2H, m); IR: 2964, 2922, 2852, 1597,1490, 1468, 1410, 1384, 1168, 1132, 1083, 1010, 813 cm⁻¹ ; MS: 328 M!⁺,326 M!⁺, 185, 183, 157, 155.

EXAMPLE 13

2-(4'-Bromophenyl)-5-n-heptyl-1,3-dioxane

Quantities: compound from Example 8 (44 g, 0.25 mol),4-bromobenzaldehyde (42.8 g, 0.23 mol) and 4-toluenesulphonic acid (150mg). The experimental procedure was as described in Example 11.

Yield=38.8 g (49%); m.p.=59.0°-59.5° C.; ¹ H NMR (CDCl₃): δ0.90 (3H, t),1.09 (2H, q) 1.30 (10H, m), 2.12 (1H, m), 3.52 (2H, t), 4.23 (2H, q),5.38 (1H, s), 7.30 (2H, s), 7.30 (2H, m), 7.49 (2H, m); IR: 2962, 2934,2864, 1600, 1492, 1474, 1389, 1168, 1132, 1087, 1030, 1010, 808 cm⁻¹ ;MS: 342 M!⁺, 340 M!⁺, 185, 183.

EXAMPLE 14

2-(4'-Bromophenyl)-5-n-octyl-1,3-dioxane

Quantities: compound from Example 9 (48.3 g, 0.26 mol),4-bromobenzaldehyde (46.5 g, 0.25 mol) and 4-toluenesulphonic acid (150mg). The experimental procedure was as described in Example 11.

Yield=57 g (64%); m.p.=50.5°-51.0° C.; ¹ H NMR (CDCl₃): δ0.89 (3H, t),1.09 (2H, q), 1.27 (12H, m), 2.12 (1H, m), 3.51 (2H, t), 4.22 (2H, q),5.36 (1H, s), 7.36 (2H, m), 7.49 (2H, m); IR: 2958, 2922, 2854, 1600,1468, 1418, 1387, 1150, 1127, 1081, 1013, 822 cm⁻¹ ; MS: 356 M!⁺, 354M!³⁰, 185, 183.

EXAMPLE 15

2-(4'-Bromophenyl)-5-n-nonyl-1,3-dioxane

Quantities: compound from Example 10 (40.5 g, 0.2 mol),4-bromobenzaldehyde (37 g, 0.2 mol) and 4-toluenesulphonic acid (150mg). The experimental procedure was as described in Example 11.

Yield=33 g (45%); m.p.=53.0°-54.0° C.; ¹ H NMR (CDCl₃): δ0.90 (3H, t),1.10 (2H, q) 1.30 (14H, m), 2.10 (1H, m), 3.52 (2H, m), 4.23 (2H, m),5.36 (1H, s), 7.36 (2H, m), 7.50 (2H, m); IR: 2962, 2930, 2860, 1602,1500, 1468, 1407, 1388, 1172, 1133, 1089, 1016, 812 cm⁻¹ ; MS: 370 M!⁺,368 M!⁺, 185, 183.

EXAMPLE 16

1-(2,3 -Difluorophenyl)pentan-1-ol

n-Butyllithium (50 cm³, 10.0M in hexanes, 0.5 mol) was added dropwise toa stirred, cooled (-78° C.) solution of 1,2-difluorobenzene (57 g, 0.5mol) in dry THF (600 cm³) under an atmosphere of dry nitrogen. Themixture was maintained under these conditions (3 h) then a solution ofpentanal (43.1 g, 0.5 mol), in dry THF (50 cm³) added dropwise at -78°C. The temperature of the reaction mixture was allowed to reach roomtemperature overnight. An aqueous solution of ammonium chloride (27 g in160 cm³ water) was added and the product extracted into diethyl ether(2×150 cm³), the combined extracts washed with water (2×150 cm³) anddried (MgSO₄). The solvent was removed in vacuo to give the product as acolourless oil which was purified by distillation under reducedpressure.

Yield=55.5 g (55%); b.p.=94°-98° C./1.0 mm Hg; ¹ H NMR (CDCl₃): δ0.90(3H, t), 1.35 (4H, m), 1.77 (2H, m), 1.92 (1H, s), 5.03 (1H, t), 7.07(2H, m), 7.22 (1H, m); IR: 3600-3100, 2964, 2938, 2870, 1631, 1601,1487, 1278, 1205, 1060, 826, 787, 730 cm⁻¹ ; MS: 200 M!⁺, 142.

EXAMPLE 17

(2,3-Difluorophenyl)hexan-1-ol

Quantities: n-butyllithium (31 cm³, 10.0M in hexanes, 0.31 mol), hexanal(31.5 g, 0.31 mol) and 1,2-difluorobenzene (35.5 g, 0.31 mol). Theexperimental procedure was as described in Example 16.

Yield=52.6 g (79%); b.p.=98°-102° C./0.5 mm Hg; ¹ H NMR (CDCl₃): δ0.88(3H, t), 1.30 (6H, m), 1.77 (2H, q), 1.98 (1H, s), 5.02 (1H, t), 7.07(2H, m), 7.22 (1H, m); IR: 3600-3100, 2968, 2940, 2872, 1630, 1600,1487, 1277, 1207, 1060, 923, 826, 790, 730 cm⁻¹ ; MS: 213 M-1!⁺, 142.

EXAMPLE 18

1-(2,3-Difluorophenyl)heptan-1-ol

Quantities: n-butyllithium (50 cm³, 10.0M in hexanes, 0.5 mol), heptanal(57 g, 0.5 mol) and 1,2-difluorobenzene (57 g, 0.5 mol). Theexperimental procedure was as described in Example 16.

Yield=93.2 g (82%); b.p.=100°-104° C./0.2 mm Hg; ¹ H NMR (CDCl₃): δ0.90(3H, t), 1.31 (8H, m), 1.78 (2H, q), 2.08 (1H, s), 5.01 (1H, t), 7.07(2H, m), 7.21 (1H, m); IR: 3600-3100, 2960, 2932, 2860, 1628, 1600,1489, 1280, 1205, 1065, 926, 825, 787, 728 cm⁻¹ ; MS: 228 M!⁺, 210, 143.

EXAMPLE 19

1 -(2,3-Difluorophenyl)octan-1-ol

Quantities: n-butyllithium (30 cm³, 10.0M in hexanes, 0.3 mol), octanal(38.5 g, 0.3 mol) and 1,2-difluorobenzene (34.5 g, 0.3 mol). Theexperimental procedure was as described in Example 16.

Yield=53.3 g (73%); b.p.=108°-110° C./0.15 mm Hg; ¹ H NMR (CDCl₃): δ0.87(3H, t), 0-1.27 (10H, m), 1.77 (2H. 18q), 1.87 (1H, s), 5.03 (1H, t),7.07 (2H, m), 7.22 (1H, m); IR: 3600-3100, 2964, 2938, 2864, 1630, 1602,1490, 1280, 1208, 1067, 827, 790, 730 cm⁻¹ ; MS: 242 M!⁺, 224, 142.

EXAMPLE 20

1-(2,3-Difluorophenyl)nonan-1-ol

Quantities: n-butyllithium (50 cm³, 10.0M in hexanes, 0.5 mol), nonanal(71 g, 0.5 mol) and 1,2-difluorobenzene (57 g, 0.5 mol). Theexperimental procedure was as described in Example 16.

Yield=86.7 g (68%); b.p.=128°-130° C./0.6 mm Hg; ¹ H NMR (CDCl₃): δ0.90(3H, t); 1.30 (12H, m), 1.76 (2H, q), 1.98 (1H, s), 5.02 (1H, t), 7.06(2H, m), 7.25 (1H, m); IR: 3600-3100, 2930, 2860, 1630, 1600, 1487,1275, 1205, 1063, 825, 790, 727 cm⁻¹ ; MS: 256 M!⁺, 238, 143.

EXAMPLE 21

(2,3-Difluorophenyl)decan-1-ol

Quantities: n-butyllithium (30 cm³, 10.0M in hexanes, 0.3 mol), decanal(47 g, 0.3 mol) and 1,2-difluorobenzene (34.5 g, 0.3 mol). Theexperimental procedure was as described in Example 16.

Yield=56.4 g (70%): b.p.=118°-123° C./0.15 mm Hg: ¹ H NMR (CDCl₃): δ0.88(3H, t), 1.27 (14H, m), 1.77 (2H, q), 1.87 (1H, s), 5.03 (1H, t), 7.06(2H, m), 7.22 (1H, m); IR: 3600-3100, 2934, 2864, 1632, 1602, 1488,1280, 1207, 1065, 827, 790, 730 cm⁻¹ ; MS: 270 M!⁺, 252, 142.

EXAMPLE 22

2,3-Difluoro-1-pentylbenzene

A solution of compound from Example 16 (55.5 g, 0.28 mol) in lightpetrol (100 cm³) was added dropwise to a stirred mixture of phosphoruspentoxide (127 g, 0.9 mol) in light petrol (300 cm³). The mixture wasstirred overnight at room temperature (GLC analysis revealed reaction tobe complete) and then filtered. 5% Palladium-on-charcoal (7 g) was addedto the filtrate and the mixture was stirred under an atmosphere ofhydrogen (12 h) at room temperature and pressure (GLC analysis revealedreaction to be complete). The palladium-on-charcoal was filtered off andthe solvent was removed in vacuo to give the product as a colourless oilwhich was purified by distillation under reduced pressure.

Yield=29.2 g (57%); b.p.=50°-52° C./0.85 mm Hg; ¹ H NMR (CDCl₃): δ0.90(3H, t), 1.35 (4H, m), 1.62 (2H, q), 2.67 (2H, t), 6.96 (3H, m); IR:2964, 2938, 2868, 1630, 1600, 1489, 1286, 1210, 1109, 1058, 827, 782,728 cm¹ ; MS: 184 M!⁺, 127.

EXAMPLE 23

2,3-Difluoro-1-hexylbenzene

Quantities: compound from Example 17 (52.6 g, 0.25 mol), phosphoruspentoxide (105 g, 0.74 mol) and 5% palladium-on-charcoal (5.8 g). Theexperimental procedure was as described in Example 22.

Yield=27.2 g (56%); b.p.=48°-56° C./0.2 mm Hg; ¹ H NMR (CDCl₃): δ0.88(3H, t), 1.31 (6H, m), 1.60 (2H, q), 2.66 (2H, sex), 6.96 (3H, m); IR:2970, 2940, 2870, 1630, 1600, 1490, 1286, 1212, 830, 782, 730 cm¹ ; MS:198 M!⁺, 169, 155, 141, 127.

EXAMPLE 24

2,3-Difluoro-1-heptylbenzene

Quantities: compound from Example 18 (93.2 g, 0.41 mol), phosphoruspentoxide (174 g, 1.2 mol) and 5% palladium-on-charcoal (4.6 g). Theexperimental procedure was as described in Example 22.

Yield=30.1 g (35%); b.p.=73°-75° C./0.6 mm Hg; ¹ H NMR (CDCl₃): δ0.90(3H, t), 1.33 (8H, m), 1.62 (2H, q), 2.67 (2H, t), 6.97 (3H, m); IR:3001, 2972, 2902, 1647, 1614, 1509, 1303, 1228, 841, 798, 746 cm⁻¹ ; MS:212 M!⁺, 169, 140, 127.

EXAMPLE 25

2,3-Difluoro-1-octylbenzene

Quantities: compound from Example 19 (53.3 g, 0.22 mol), phosphoruspentoxide (95 g, 0.67 mol) and 5% palladium-on-charcoal (5.5 g). Theexperimental procedure was as described in Example 22.

Yield=31 g (62%); b.p.=72°-79° C./0.15 mm Hg; ¹ H NMR (CDCl₃): δ0.90(3H, t), 1.30 (10H, m), 1.60 (2H, q), 2.65 (2H, t), 6.96 (3H, m); IR:2968, 2934, 2864, 1633, 1600, 1488, 1285, 1213, 830, 782, 728 cm⁻¹ ; MS:226 M!⁺, 183, 169, 155, 141, 128.

EXAMPLE 26

2,3-Difluoro-1-nonylbenzene

Quantities: compound from Example 20 (84.6 g, 0.33 mol), phosphoruspentoxide (142 g, 1mol) and 5% palladium-on-charcoal (7 g). Theexperimental procedure was as described in Example 22.

Yield=59.1 g (75%); b.p.=100°-105° C./0.4 mm Hg; ¹ H NMR (CDCl₃): δ0.88(3H, t), 1.26 (12H, m), 1.60 (2H, q), 2.65 (2H, sex), 6.95 (3H, m); IR:2972, 2942, 2872, 1636, 1605, 1495, 1288, 1217, 830, 785, 733 cm¹ ; MS:240 M!⁺, 128.

EXAMPLE 27

2,3-Difluoro-1-decylbenzene

Quantities: compound from Example 21 (56.4 g, 0.21 mol), phosphoruspentoxide (74.5 g, 0.53 mol) and 5% palladium-on-charcoal (4.58). Theexperimental procedure was as described in Example 22.

Yield=26.6 g (50%); b.p.=105°-112° C./0.6 mm Hg; ¹ H NMR (CDCl₃): δ0.88(3H, t), 1.26 (14H, m), 1.60 (2H, q), 2.65 (2H, sex), 6.96 (3H, m); IR:2966, 2930, 2864, 1630, 1600, 1490, 1287, 1213, 830, 782, 730 cm⁻¹ ; MS:254 M!⁺, 218, 199, 168, 140, 128, 126.

EXAMPLE 28

4-n-Pentyl-2,3-difluorophenyl boronic acid

n-Butyllithium (10 cm³, 10M in hexanes, 0.1 mol) was added dropwise to astirred, cooled (-78° C.) solution of the compound from Example 22 (17.3g, 94 m mol) in dry THF (250 cm³) under an atmosphere of dry nitrogen.The reaction mixture was stirred (2.5 h) then a previously cooled (-78°C.) solution of triisopropyl borate (35.7 g, 0.19 mol) in dry THF (70cm³) added dropwise at -78° C. The reaction mixture was allowed to warmto room temperature overnight then stirred (1h) with hydrochloric acid(10%, 100 cm³). The product was extracted into diethyl ether (2×100cm³), and the combined extracts washed with water and dried (MgSO₄). Thesolvent was removed in vacuo to yield colourless crystals.

Yield=21 g (98%); ¹ H NMR (CDCl₃): δ0.90 (3H, t), 1.33 (4H, m), 1.62(2H, q), 2.68 (2H, t), 4.97 (2H, band), 7.00 (1H, m), 7.46 (1H, m); IR:3600-3000, 2962, 2940, 2870, 1636, 1497, 1455, 1355, 1220, 1133, 1056,996, 905, 815 cm⁻¹ ; MS: 630 M!⁺ (trimer), 574, 505, 448, 391, 378, 322,228 M!⁺ (monomer).

EXAMPLE 29

4-n-Hexyl-2,3-difluorophenyl boronic acid

Quantities: compound from Example 23 (27.78, 0.14 mol), n-butyllithium(14 cm³, 10.0M in hexanes, 0.14 mol) and triisopropyl borate (52.7 g,0.28 mol). The experimental procedure was as described in Example 28.

Yield=33.8 g (100%); ¹ H NMR (CDCl₃): δ0.90 (3H, t), 1.30 (6H, m), 1.62(2H, q), 2.70 (2H, t), 3.77 (2H, t), 7.00 (1H, m), 7.45 (1H, m); IR:3700-3000, 2968, 2932, 2860, 1635, 1497, 1455, 1385, 1354, 1220, 1208,1131, 903, 835 cm⁻¹ ; MS: 242 M!⁺, 214, 198, 172.

EXAMPLE 30

4-n-Heptyl-2,3-difluorophenyl boronic acid

Quantities: compound from Example 24 (31.4 g, 0.15 mol), n-butyllithium(15 cm³, 10.0M in hexanes, 0.15 mol) and triisopropyl borate (56.4 g,0.3 mol). The experimental procedure was as described in Example 28.

Yield=38 g (99%); ¹ H NMR (CDCl₃): δ0.90 (3H, m), 1.30 (8H, m), 1.63(2H, m) 2.67 (2H, t), 4.08 (2H, band), 7.00 (1H, m), 7.45 (1H, m); IR:3600-3000, 2960, 2930, 2864, 1637, 1455, 1205, 1133, 957, 902 cm⁻¹ ; MS:256 M!⁺, 228, 205, 170.

EXAMPLE 31

4-n-Octyl-2,3-difluorophenyl boronic acid

Quantities: compound from Example 25 (31 g, 0.14 mol), n-butyllithium(14 cm³, 10.0M in hexanes, 0.14 mol) and triisopropyl borate (52.7 g,0.28 mol). The experimental procedure was as described in Example 28.

Yield=37.5 g (99%); 1H NMR (CDCl₃): δ0.90 (3H, t), 1.32 (10H, m), 1.63(2H, q), 2.67 (2H, sex), 5.13 (2H, band), 7.00 (1H, m), 7.46 (1H, m);IR: 3700-3000, 2958, 2920, 2852 1640, 1452, 1223, 1192, 1158, 1020, 955,901, 832 cm⁻¹ ; MS: 270 M!+, 242, 226, 172.

EXAMPLE 32

4-n-Nonyl-2,3-difluorophenyl boronic acid

Quantities: compound from Example 26 (35.5 g, 0.15 mol), n-butyllithium(15 cm³, 10M in hexanes, 0.15 mol) and triisopropyl borate (56.4 g, 0.3mol). The experimental procedure was as described in Example 28.

Yield=42.6 g (100%): ¹ H NMR (CDCl₃): δ0.90 (3H, t), 1.27 (12H, m), 1.62(2H, q), 2.67 (2H, sex), 4.05 (2H, band), 7.00 (1H, m), 7.46 (1H, m);IR: 3700-3000, 2960, 2930, 2858, 1636, 1500, 1456, 1360, 1220, 1200, 905cm⁻¹ : MS: 284 M!⁺, 240, 127.

EXAMPLE 33

4-n-Decyl-2,3-difluorophenyl boronic acid

Quantities: compound from Example 27 (26.7 g, 105 mmol), n-butyllithium(11 cm³, 10.0M in hexanes, 0.11 mol) and triisopropyl borate (39.5 g,0.21 mol). The experimental procedure was as described in Example 28.

Yield=31 g (99%); ¹ H NMR (CDCl₃): δ0.88 (3H, t), 1.26 (14H, m), 1.61(2H, q) 2.68 (2H, sex), 4.95 (2H, m), 7.00 (1H, m), 7.45 (1H, m); IR:3600-3100, 2960, 2920, 2854, 1642, 1452, 1392, 1355, 1225, 1158, 1120,1023, 954, 901, 830 cm⁻¹ ; MS: 298 M!⁺, 254, 171, 127.

EXAMPLE 34

2,3-Difluoro-1-(2'-methyl hexoxy) benzene

In the absence of moisture and under an atmosphere of dry nitrogen,diethyl azodicarboxylate (20.4 g, 0.12 mol) was added dropwise to astirred solution of triphenylphosphine (31.5 g, 0.12 mol), 2methyl-hexanol (13.9 g, 0.12 mol) and 2,3-difluorophenol (13 g, 0.1 mol)in dry THF (220 cm³) at room temperature. The reaction mixture wasstirred overnight at room temperature until GLC and TLC analysisrevealed complete reaction. The solvent was removed in vacuo and diethylether (200 cm³) added. The precipitate was filtered out and the solventremoved from the filtrate in vacuo. Flash column chromatography (lightpetrol/ethyl acetate: 49:1) give the product as a colourless oil.

Yield=22.4 g (98%); ¹ H NMR (CDCl₃): δ0.93 (3H, m), 1.04 (3H, d), 1.33(4H, m), 1.51 (2H, m), 1.97 (1H, sex), 3.79 (1H, q), 3.89 (1H, q), 6.74(2H, m), 6.95 (1H, m); IR: 2954, 2920, 2866, 1619, 1509, 1479, 1314,1250, 1170, 762, 704 cm⁻¹ : MS: 228 M!⁺, 129, 56.

EXAMPLE 35

(2-Methylhexoxy)-2,3-difluorophenylboronic acid

Quantities: compound from Example 34 (11.4 g, 50 mmol), n-butyllithium(5 cm³, 10.0M in hexanes, 50 mmol) and triisopropyl borate (18.8 g, 0.1mol). The experimental procedure was as described in Example 28.

Yield=13.6 g (100%); ¹ H NMR (CDCl₃): δ0.92 (3H, sex), 1.04 (3H, d),1.34 (4H, m), 1.52 (2H, m), 1.98 (1H, sex), 3.83 (1H, q), 3.93 (1H, q),6.76 (1H, m), 7.46 (1H, m); IR: 3700-3100, 2978, 2880, 1636, 1527, 1477,1363, 1308, 1233, 1089, 1038, 910, 824 cm⁻¹ ; MS: 468, 286, 130.

EXAMPLE 36

2,3-Difluorophenylboronic acid

n-Butyllitium (30 cm³, 10M in hexanes, 0.3 mol) was added dropwise to astirred, cooled (-78° C.) solution of 1,2-difluorobenzene (34.5 g, 0.3mol) in dry THF (350 cm³) under a atmosphere of dry nitrogen. Thereaction mixture was stirred (2.5 h) then a previously cooled (-78° C.)solution of triisopropyl borate (113 g, 0.6 mol) in dry THF (200 cm³)added dropwise at -78° C. The reaction mixture was allowed to warm toroom temperature overnight then stirred (1 h) with hydrochloric acid(10%, 300 cm³). The product was extracted into diethyl ether (2×300cm³), and the combined extracts washed with water and dried (MgSO₄). Thesolvent was removed in vacuo to yield colourless crystals.

Yield=47 g (100%); ¹ H NMR (CDCl₃): δ5.10 (2H, d), 7.16 (1H, m), 7.28(1H, m), 7.57 (1H, m); IR: 3700-3000, 1628, 1472, 1360, 1270, 1048, 908cm⁻¹ ; MS: 158 M!⁺, 140, 114.

EXAMPLE 37

2,3-Difluorophenol

Hydrogen peroxide (10%, 340 cm³, 1 mol) was added dropwise to a stirredsolution of compound from Example 36 (47 g, 0.3 mol) in diethyl ether(350 cm³) heated under reflux. The stirred mixture was heated underreflux for a further 2.5 h then cooled. The ethereal layer was separatedand the aqueous layer extracted with diethyl ether (2×200 cm³). Thecombined ethereal layers were washed with sodium hydroxide (10%, 4×100cm³) and the separated aqueous layers acidified with 36% hydrochloricacid. The product was extracted into diethyl ether (3×100 cm³), and thecombined ethereal extracts washed with water and dried (MgSO₄). Thesolvent was removed in vacuo to give an off white solid.

Yield=39 g (100%); m.p.=30°-32° C.; ¹ H NMR (CDCl₃): δ5.15 (1H, d),6.67-6.82 (2H, m), 6.90-7.00 (1H, m); IR: 3700-3000, 1630, 1535, 1513,1492, 1482, 1360, 1310, 1255, 1182, 1025, 910, 736 cm⁻¹ ; MS: 130 M!⁺,121.

EXAMPLE 38

2,3-Difluoro-1-n-petoxybenzene

A solution of 1-bromopentane (30.5 g, 0.2 mol) in acetone (50 cm³) wasadded dropwise to a stirred mixture of compound from Example 37 (26 g,0.2mol) and potassium carbonate (55.5 g, 0.4 mol) in acetone (200 cm³)at room temperature. The stirred mixture was heated under reflux (43 h)(i.e. until glc analysis revealed a complete reaction), the solutionpoured into water (600 cm³), and the crude product extracted intodiethyl ether (2×200 cm³) and dried (Na₂ SO₄). The solvent was removedin vacuo and the pure product obtained by distillation under reducedpressure as a colourless liquid.

Yield=37 g (92%); b.p.=75°-78° C./0.6 mm Hg; ¹ H NMR (CDCl₃): δ0.93 (3H,t), 1.43 (4H, m), 1.83 (2H, q), 4.03 (2H, t), 6.74 (2H, m), 6.96 (1H,m); IR: 2968, 2942, 2882, 1624, 1517, 1487, 1473, 1322, 1294, 1257,1076, 768, 710 cm⁻¹ ; MS: 200 M!⁺, 130.

EXAMPLE 39

2,3-Difluoro-1-n-hexoxybenzene

Quantities: 1-bromohexane (50 g, 0.3 mol), potassium carbonate (83 g,0.6mol) and compound from Example 37 (39 g, 0.3 mol). The experimentalprocedure was as described in Example 38.

Yield=52.3 g (81%); b.p.=94°-98° C./0.7 mm Hg: ¹ H NMR (CDCl₃): δ0.89(3H, t), 1.33 (4H, m), 1.45 (2H, q), 1.83 (2H, q), 4.03 (2H, t), 6.74(2H, m), 6.96 (1H, m); IR: 2960, 2916, 2888, 1624, 1513, 1484, 1470,1319, 1292, 1254, 1080, 766, 708 cm⁻¹ ; MS: 214 M!⁺, 130.

EXAMPLE 40

2,3-Difluoro-1-n-heptoxybenzene

Quantities: 1-bromoheptane (46.6 g, 0.26 mol), potassium carbonate (70g, 0.5 mol) and compound from Example 37 (31.2 g, 0.24 mol). Theexperimental procedure was as described in Example 38.

Yield=48.5 g (89%); b.p.=119°-120° C./1 mm Hg; ¹ H NMR (CDCl₃): δ0.90(3H, t), 1.30 (6H, m), 1.45 (2H, q), 1.80 (2H, q), 4.00 (2H, t), 6.74(2H, m), 6.95 (1H, m); IR: 2960, 2940, 2880, 2860, 1625, 1520, 1485,1472, 1320, 1295, 1255, 1080, 770, 710 cm⁻¹ ; MS: 228 M!⁺, 130.

EXAMPLE 41

2,3-Difluoro-1-n-octoxybenzene

Quantities: 1-bromooctane (34.9 g, 0.18 mol), potassium carbonate (50 g,0.36 mol) and compound from Example 37 (21.7 g, 0.17 mol). Theexperimental procedure was as described in Example 38.

Yield=33.7 g (83%); b.p.=94°-99° C./0.25 mm Hg; ¹ H NMR (CDCl₃): δ0.89(3H, t), 1.30 (8H, m), 1.45 (2H, q), 1.82 (2H, q), 4.02 (2H, t), 6.74(2H, m), 6.96 (1, m); IR: 2940, 2864, 1622, 1518, 1485, 1472, 1322,1295, 1257, 1080, 769, 710 cm⁻¹ MS: 242 M!⁺, 130.

EXAMPLE 42

2,3-Difluoro-1-n-nonoxybenzene

Quantities: 1-bromnononae (55.2 g, 0.27 mol), potassium carbonate (70 g,0.5 mol) and compound from Example 37 (31.2 g, 0.24 mol). Theexperimental procedure was as described in Example 38.

Yield=55.68 (90%); b.p.=100°-105° C./0.05 mm Hg; ¹ H NMR (CDCl₃): δ0.90(3H, t), 1.30 (10H, m), 1.45 (2H, q), 1.80 (2H, q), 4.00 (2H, t), 6.74(2H, m), 6.95 (1H, m); IR: 2935, 2860, 1625, 1520, 1485, 1472, 1322,1295, 1257, 1080, 770, 710 cm⁻¹ ; MS: 256 M!⁺, 130.

EXAMPLE 43

2,3-Difluoro-4-n-pentoxyphenylboronic acid

Quantities: n-butyllithium (20 cm³, 10.0M in hexanes, 0.2 mol), compoundfrom Example 38 (378, 0.19 mol) and triisopropyl borate (708, 0.38 mol).The experimental procedure was as described in Example 28.

Yield=458 (100%); ¹ H NMR (CDCl₃): δ0.94 (3H, t), 1.42 (4H, m), 1.84(2H, q), 3.15 (2H, band), 4.07 (2H, t), 6.77 (1H, m), 7.44 (1H, m); IR:3700-3000, 2960, 2940, 2870, 1630, 1520, 1470, 1365, 1306, 1222, 1084,1030, 908, 820, 790, 747 cm⁻¹ ; MS: (180° C.); 678 M!⁺ (trimer), 468,(120° C.); 244 M!⁺ (monomer), 174, 130.

EXAMPLE 44

2,3-Difluoro-4-n-hexoxyphenylboronic acid

Quantifies: n-butyllithium (15 cm³, 10.0M in hexanes, 0.15 mol),compound in Example 39 (31 g, 0.15 mol) and triisopropyl borate (56 g,0.3 mol). The experimental procedure was as described in Example 28.

Yield=398 (100%); ¹ H NMR (CDCl₃): δ0.91 (3H, t), 1.35 (4H, m), 1.47(2H, m), 1.82 (2H, q), 4.06 (2H, t), 6.77 (1H, m), 7.44 (1H, m), noobvious OH absorption: IR: 3700-3000, 2964, 2940, 2868, 1630, 1522,1472, 1365, 1308, 1225, 1082, 1033, 821, 790, cm⁻¹ ; MS: 720 M!⁺(trimer), 636, 552, 468.

EXAMPLE 45

2,3-Difluoro-4-n-heptoxyphenylboronic acid

Quantities: n-butyllithium (20 cm³, 10.0M in hexanes, 0.2 mol), compoundfrom Example 40 (45.5 g, 0.2 mol) and triisopropyl borate (74.4 g, 0.4mol). The experimental procedure was as described in Example 28.

Yield=54 g (100%); ¹ H NMR (CDCl₃): δ0.90 (3H, t), 1.30 (6H, m), 1.45(2H, q), 1.80 (2H, q), 4.05 (2H, t), 4,85 (2H, d), 6.78 (1H, m), 7.48(1H, m); IR: 3600-3000, 2960, 2930, 2860, 1628, 1520, 1462, 1360, 1304,1222, 1085, 1035, 820 cm⁻¹ ; MS: 272 M!⁺, 174, 146.

EXAMPLE 46

2,3-Difluoro-4-n-octoxyphenylboronic acid

Quantities: n-butyllithium (10 cm³, 10.0M in hexanes, 0.1 mol), compoundfrom Example 41 (23.4 g, 0.1 mol) and triisopropyl borate (37.6 g, 0.2mol). The experimental procedure was as described in Example 28.

Yield=29 g (100%); ¹ H NMR (CDCl₃): δ0.90 (3H, t), 1.30 (8H, m), 1.45(2H, q), 1.83 (2H, q), 4.07 (2H, t), 4.90 (1H, band), 6.78 (1H, m), 7.48(1H, m); IR: 3700-3000, 2970, 2940, 2868, 1631, 1523, 1471, 1365, 1310,1227, 1090, 1035, 908, 820, 788, 749 cm⁻¹ ; MS: 636, 468, 286 M!⁺, 268,242.

EXAMPLE 47

2,3-Difluoro-4-n-nonoxyphenylboronic acid

Quantities: n-butyllithium (20 cm³, 10.0M in hexanes, 0.2 mol), compoundfrom Example 42 (51.6 g, 0.2 mol) and triisopropyl borate (74.4 g, 0.2mol). The experimental procedure was as described in Example 28.

Yield=60 g (100%); ¹ H NMR (CDCl₃): δ0.88 (3H, t), 1.29 (10H, m), 1.45(2H, q), 1.82 (2H, q), 2.18 (2H, s), 4.07 (2H, t), 6.78 (1H, m), 7.48(1H, m); IR: 3700-3000, 2960, 2922, 2852, 1633, 1522, 1470, 1367, 1306,1215, 1083, 820 cm⁻¹ ; MS: 300 M!⁺, 271, 256.

EXAMPLE 48

2-(4"-Pentoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-pentyl-1,3-dioxane(Formula 8)

A solution of compound from Example 43 (1.34 g, 5.5 mmol) in ethanol (10cm³) was added to a vigorously stirred mixture oftetrakis(triphenylphosphine)palladium (0) (173 mg, 0.15 mmol), aqueoussodium carbonate (5 ml, 2M) and compound from Example 11 (1.57 g, 5mmol) in benzene (15 cm³). The reaction mixture was heated under reflux(23 h) then cooled to room temperature. Excess boronic acid was oxidizedusing 27% hydrogen peroxide (0.5 cm³) over a period of 1 h. The mixturewas extracted with diethyl ether (2×50 cm³), and the ethereal extractswashed with saturated aqueous sodium chloride (2×50 cm³) and dried (Na₂SO₄). The solvent was removed in vacuo and the product purified by flashcolumn chromatography (dichloromethane/light petrol: 1:1 ) andrecrystallisation from methanol/light petrol (1:1).

Yield=1.6 g (74%); Purity (HPLC): 99.84%; Mesomorphism (T/°C.): K 64.5SmC 81.4N 140.4 Iso; ¹ H NMR (CDCl₃): δ0.90 (3H, t), 0.95 (3H, t), 1.11(2H, q), 1.29 (8H, m), 1.45 (2H, m), 1.85 (2H, q), 2.14 (1H, m), 3.55(2H, m), 4.07 (2H, t), 4.25 (2H, q), 5.46 (1H, s), 6.78 (1H, m), 7.07(1H, m), 7.53 (4H, m); IR: 2966, 2932, 2864, 1630, 1510, 1472, 1388,1320, 1303, 1294, 1128, 1081, 1021, 800 cm⁻¹ ; MS: 432 M!⁺, 361, 234.

EXAMPLE 49

2-(4"-Hexoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-pentyl-1,3-dioxane

Quantities: compound from Example 11 (1.57 g, 5 mmol), compound fromExample 44 (1.35 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.4 g (63%); Purity (HPLC); 99.29%; Mesomorphism (T/°C.): K 62.0SmC 81.1 N 139.9 Iso; ¹ H NMR (CDCl₃): δ0.93 (6H, q), 1.12 (2H, q), 1.31(8H, m), 1.36 (2H, m), 1.49 (2H, q), 1.85 (2H, q), 2.15 (1H, m), 3.56(2H, t), 4.08 (2H, t), 4.26 (2H, q), 5.46 (1H, s), 6.79 (1H, m), 7.08(1H, m), 7.54 (4H, m); IR: 2962, 2936, 2860, 1630, 1510, 1474, 1412,1388, 1320, 1302, 1293, 1228, 1210, 1181, 1023, 800 cm⁻¹ ; MS: 446 M!⁺,361, 234.

EXAMPLE 50

2-(4"-Heptoxy-2",3"-difluorobiphenyl-4-yl)-5-n-pentyl-1,3-dioxane

Quantities: compound from Example 11 (1.57 g, 5 mmol), compound fromExample 45 (1.54 g, 5.7 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.3 g (56%); Purity (HPLC): 99.93%; Mesomorphism (T/°C.): K 62.5SmC 85.1N 134.6 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, t), 1.11 (2H, q), 1.31(12H, m), 1.46 (2H, m), 1.84 (2H, q), 2.14 (1H, m), 3.56 (2H, t), 4.07(2H, t), 4.25 (2H, q), 5.46 (1H, s), 6.78 (1H, m), 7.07 (1H, m), 7.53(4H, m): IR: 2962, 2932, 2860, 1630, 1509, 1473, 1388, 1321, 1293, 1128,1079, 1022, 801 cm⁻¹ ; MS: 460 M!⁺, 361, 234.

EXAMPLE 51

2-(4"-Octoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-pentyl-1,3-dioxane

Quantities: compound from Example 11 (1.57 g, 5 mmol), compound fromExample 46 (1.57 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.4 g (59%); Purity (HPLC): 99.94%; Mesomorphism (T/°C.): K 62.0SmC 85.8N 133.9 Iso; ¹ H NMR (CDCl₃): δ0.89 (6H, sex), 1.11 (2H, q),1.30 (14H, m), 1.48 (2H, q), 1.84 (2H, q), 2.14 (1H, m), 3.56 (2H, t),4.07 (2H, t), 4.26 (2H,q), 5.46 (1H, s), 6.78 (1H, m), 7.07 (1H, m),7.53 (4H, m); IR: 2960, 2926, 2856, 1630, 1510, 1470, 1413, 1388, 1320,1292, 1229, 1080, 1024, 800 cm⁻¹ ; MS: 474 M!⁺, 361, 234.

EXAMPLE 52

2-(4"-Nonoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-pentyl-1,3-dioxane

Quantities: compound from Example 11 (1.57 g, 5 mmol), compound fromExample 47 (1.65 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.0 g (41%); Purity (HPLC): 99.67%; Mesomorphism (T/°C.): K 62.5SmC 86.9N 129.3 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, sex), 1.11 (2H, q),1.30 (16H, m), 1.46 (2H, q), 1.84 (2H, q), 2.15 (1H, m), 3.56 (2H, t),4.09 (2H, t), 4.26 (2H, q), 5.48 (1H, s), 6.78 (1H, m), 7.07 (1H, m),7.54 (4H, m); IR: 2960, 2928, 2856, 1628, 1527, 1509, 1469, 1391, 1312,1302, 1290, 1190, 1130, 1105, 1076, 1019, 805 cm⁻¹ ; MS: 488 M!⁺, 361,234.

EXAMPLE 53

2-(4"-Pentyl-2",3"-difluorobiphenyl-4'-yl)-5-n-pentyl-1,3-dioxane

Quantities: compound from Example 11 (1.57 g, 5 mmol), compound fromExample 28 (1.2 g, 5.25mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.5 g (72%); Purity (HPLC): 100.00%; Mesomorphism (T/°C.): K 64.5119.6 Iso N 119.4 43.1 SmC; ¹ H NMR (CDCl₃): δ0.93 (6H, q), 1.12 (2H,q), 1.31 (10H, m), 1.65 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.56 (2H,t), 4.27 (2H, q), 5.48 1H, s), 6.98 (1H, m), 7.09 (1H, m), 7.58 (4H, m);IR: 2968, 2930, 2860, 1493, 1466, 1405, 1385, 1127, 1085, 1023, 813 cm⁻¹; MS: 416 M!⁺, 288, 231.

EXAMPLE 54

2-(4"-Hexyl-2",3"-difluorobiphenyl-4'-yl)-5-n-pentyl-1,3-dioxane

Quantities: compound from Example 11 (1.57 g, 5 mmol), compound fromExample 29 (1.33 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.5 g (70%); Purity (HPLC): 99.95%; Mesomorphism (T/°C.): K 63.1SmC 74.9N 114.8 Iso; ¹ H NMR (CDCl₃): δ0.89 (6H, q), 1.11 (2H, q), 1.31(12H, m), 1.63 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.56 (2H, t), 4.26(2H, q), 5.46 (1H, s), 6.97 (1H, m), 7.08 (1H, m), 7.55 (4H, m); IR:2962, 2932, 2856, 1498, 1471, 1464, 1410, 1388, 1128, 1081, 1024, 812cm⁻¹ ; MS: 430 M!⁺, 359, 346, 231.

EXAMPLE 55

2-(4"-Heptyl-2",3"-difluorobiphenyl-4'-yl)-5-n-pentyl-1,3-dioxane

Quantities: compound from Example 11 (1.57 g, 5 mmol), compound fromExample 30 (1.34 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.5 g (68%); Purity (HPLC): 99.74%; Mesomorphism (T/°C.): K 67.5SmC 71.8N 111.5 Iso; ¹ H NMR (CDCl³): δ0.90 (6H, q), 1.12 (2H, q), 1.30(14H, m), 1.64 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.55 (2H, t), 4.26(2H, q), 5.47 (1H, s), 6.98 (1H, m), 7.08 (1H, m), 7.56 (4H, m); IR:2962, 2930, 2860, 1496, 1471, 1408, 1388, 1128, 1081, 1027, 812 cm⁻¹ ;MS: 444 M!⁺, 359, 345, 316, 231.

EXAMPLE 56

2-(4"-Octyl-2",3"-difluorobiphenyl-4'-yl)-5-n-pentyl-1,3-dioxane

Quantities: compound from Example 11 (1.57 g, 5 mmol), compound fromExample 31 (1.49 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.3 g (57%); Purity (HPLC): 100.0%; Mesomorphism (T/°C.): K 68.0SmC 73.5 N 110.1 Iso; ¹ H NMR (CDCl³): δ0.89 (6H, q), 1.11 (2H, q), 1.28(16H, m), 1.63 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.55 (2H, t), 4.26(2H, q), 5.48 (1H, s), 6.97 (1H, m), 7.07 (1H, m), 7.55 (4H, m); IR:2962, 2926, 2856, 1500, 1473, 1467, 1411, 1389, 1128, 1082, 1027, 812cm⁻¹ ; MS: 458 M!⁺, 359, 330, 233.

EXAMPLE 57

2-(4"-Nonyl-2",3"-difluorobiphenyl-4'-yl)-5-n-pentyl-1,3-dioxane

Quantities: compound from Example 11 (1.57 g, 5 mmol), compound fromExample 32 (1.56 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.5 g (64%); Purity (HPLC): 100.0%; Mesomorphism (T/°C.): K 75.0 N110.1 Iso; ¹ H NMR (CDCl₃): δ0.89 (6H, m), 1.11 (2H, q), 1.27 (18H, m),1.63 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.56 (2H, t), 4.26 (2H, q),5.46 (1H, s), 6.97 (1H, m), 7.08 (1H, m), 7.55 (4H, m); IR: 2960, 2924,2856, 1498, 1472, 1387, 1130, 1081, 1026, 812 cm⁻¹ ; MS: 472 M!⁺, 359,344, 231.

EXAMPLE 58

2-(4"-Decyl-2",3"-difluorobiphenyl-4'-yl)-5-n-pentyl-1,3-dioxane

Quantities: compound from Example 11 (1.57 g, 5 mmol), compound fromExample 33 (1.63 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.5 g (62%); Purity (HPLC): 99.83%; Mesomorphism (T/°C.): K 67.0SmC 70.5 N 105.0 Iso; ¹ H NMR (CDCl₃): δ0.89 (6H, q), 1.11 (2H, q), 1.27(20H, m), 1.63 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.56 (2H, t), 4.26(2H, q), 5.47 (1H, s), 6.97 (1H, m), 7.07 (1H, m),7.55 (4H, m); IR:2960, 2928, 2852, 1500, 1473, 1411, 1389, 1128, 1082, 1027, 813 cm⁻¹ ;MS: 486 M!⁺, 358, 231.

EXAMPLE 59

2-(4"-Pentoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-hexyl-1,3-dioxane

Quantities: compound from Example 12 (1.64 g, 5 mmol), compound fromExample 43 (1.34 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.3 g (58%); Purity (HPLC): 99.90%; Mesomorphism (T/°C.): K 65.5SmC 94.2 N 135.5 Iso: ¹ H NMR (CDCl₃): δ0.89 (6H, sex), 1.12 (2H, q),1.31 (10H, m), 1.45 (2H, q). 1.85 (2H, q), 2.15 (1H, m), 3.56 (2H, t),4.08 (2H, t), 4.25 (2H, q), 5.45 (1H, s), 6.78 (1H, m), 7.07 (1H, m),7.53 (4H, m); IR: 2964, 2938, 2862, 1630, 1530, 1510, 1474, 1412, 1388,1320, 1302, 1293, 1129, 1082, 1065, 1025, 801 cm⁻¹ ; MS: 446 M!⁺, 375,234.

EXAMPLE 60

2-(4"-Hexoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-hexyl-1,3-dioxane

Quantities: compound from Example 12 (1.64 g, 5 mmol), compound fromExample 44 (1.35 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=0.2 g (9%); Purity (HPLC): 99.63%; Mesomorphism (T/°C.): K 64.7SmC 95.6 N 135.1 Iso; ¹ H NMR (CDCl₃): δ0.91 (6H, q), 1.12 (2H, q), 1.31(10H, m), 1.36 (2H, m), 1.49 (2H, q), 1.85 (2H, q), 2.15 (1H, m), 3.56(2H, t), 4.08 (2H, t), 4.25 (2H, q), 5.45 (1H, s), 6.78 (1H, m), 7.07(1H, m), 7.53 (4H, m); IR: 2964, 2934, 2860, 1630, 1507, 1470, 1411,1387, 1316, 1303, 1127, 1105, 1080, 1012, 804 cm⁻¹ ; MS: 460 M!⁺, 375,234.

EXAMPLE 61

2-(4"-Heptoxy-2",3"difluorobiphenyl-4'-yl )-5-n-hexyl-1,3-dioxane

Quantities: compound from Example 12 (1.64 g, 5 mmol), compound fromExample 45 (1.43 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=0.7 g (30%); Purity (HPLC): 100.0%; Mesomorphism (T/°C.): K 57.2SmC 99.0 N 130.9 Iso; ¹ H NMR (CDCl₃): δ0.93 (6H, t), 1.13 (2H, q), 1.33(14H, m), 1.48 (2H, q), 1.85 (2H, q), 2.15 (1H, m), 3.55 (2H, t), 4.08(2H, t), 4.26 (2H, q), 5.45 (1H, s), 6.78 (1H, m), 7.07 (1H, m), 7.53(4H, m); IR: 2960, 2934, 2862, 1630, 1508, 1470, 1388, 1316, 1303, 1128,1106, 1089, 1014, 805 cm⁻¹ ; MS: 474 M!⁺, 375, 234.

EXAMPLE 62

2-(4"-Octoxy-2",3"-difluorobiphenyl-4'yl)-5-n-hexyl-1,3-dioxane

Quantities: compound from Example 12 (1.64 g, 5 mmol), compound fromExample 46 (1.50 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.35 g (55%); Purity (HPLC): 99.21%; Mesomorphism (T/°C.): K 52.5SmC 97.7 N 129.4 Iso; ¹ H NMR (CDCl₃): δ0.93 (6H, t), 1.13 (2H, q), 1.34(16H, m), 1.49 (2H, m), 1.86 (2H, q), 2.15 (1H, m), 3.57 (2H, t), 4.08(2H, t), 4.26 (2H, q), 5.45 (1H, s), 6.78 (1H, m), 7.07 (1H, m), 7.52(4H, m); IR: 2962, 2934, 2862, 1632, 1529, 1509, 1471, 1389, 1318, 1303,1293, 1128, 1108, 1078, 1017, 801 cm⁻¹ ; MS: 488 M!⁺, 375, 234.

EXAMPLE 63

2-(4"-Nonoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-hexyl-1,3-dioxane

Quantities: compound from Example 12 (1.64 g, 5 mmol), compound fromExample 47 (1.57 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48 except for using1,2-dimethoxy ethane (20ml) instead of benzene and ethanol.

Yield=0.85 g (34%); Purity (HPLC): 99.25%; Mesomorphism (T/°C.): K 56.5SmC 86.5 N 120.0 Iso; ¹ H NMR (CDCl₃): δ0.91 (6H, q), 1.12 (2H, q), 1.31(18H, m), 1.48 (2H, q), 1.85 (2H, q), 2.15 (1H, m), 3.55 (2H, t), 4.06(2H, t), 4.25 (2H, q), 5.45 (1H, s), 6.78 (1H, m), 7.07 (1H, m), 7.53(4H, m); IR: 2960, 2924, 2858, 1636, 1528, 1509, 1477, 1405, 1390, 1303,1293, 1132, 1104, 1080, 1022, 803 cm⁻¹ ; MS: 502 M!⁺, 375, 234.

EXAMPLE 64

2-(4"-Pentyl-2",3"-difluorobiphenyl-4'-yl)-5-n-hexyl-1,3-dioxane

Quantities: compound from Example 12 (1.64 g, 5 mmol), compound fromExample 28 (1.20 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 63.

Yield=1.35 g (63%); Purity (HPLC): 99.79%; Mesomorphism (T/°C.): K 53.0SmC 71.0 SmA 91.5N 114.6 Iso; ¹ H NMR (CDCl₃): δ0.92 (6H, q), 1.13 (2H,q), 1.32 (10H, m), 1.37 (2H, m), 1.64 (2H, q), 2.15 (1H, m), 2.69 (2H,t), 3.57 (2H, t), 4.26 (2H, q), 5.46 (1H, s), 6.97 (1H, m), 7.07 (1H,m), 7.53 (4H, m); IR: 2966, 2932, 2860, 1492, 1465, 1403, 1383, 1282,1161, 1127, 1083, 1022, 812 cm⁻¹ ; MS: 430 M!⁺, 288, 231.

EXAMPLE 65

2-(4"Hexyl-2",3"-difluorobiphenyl-4'-yl)-5-n-hexyl-1,3-dioxane

Quantities: compound from Example 12 (1.64 g, 5 mmol), compound fromExample 29 (1.30 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=0.7 g (32%); Purity (HPLC): 99.55%; Mesomorphism (T/°C.): K 61.3SmC 85.0 SmA 93.0 N 111.2 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, t), 1.12 (2H,q), 1.30 (14H, m), 1.64 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.56 (2H,t), 4.25 (2H, q), 5.46 (1H, s), 6.96 (1 H, m), 7.07 (1H, m), 7.55 (4H,m); IR: 2962, 2932, 2860, 1495, 1471, 1465, 1408, 1388, 1129, 1082,1027, 813 cm⁻¹ ; MS: 444 M!⁺, 302, 231.

EXAMPLE 66

2-(4"-Heptyl-2",3"-difluorobiphenyl-4'-yl)-5-n-hexyl-1,3-dioxane

Quantities: compound from Example 12 (1.64 g, 5 mmol), compound fromExample 30 (1.34 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 63.

Yield=1.45 g (63%); Purity (HPLC): 99.77%; Mesomorphism (T/°C.): K 57.5SmC 84.5 SmA 91.8 N 108.8 Iso; ¹ H NMR (CDCl₃): δ0.89 (6H, q), 1.12 (2H,q), 1.30 (16H, m), 1.64 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.56 (2H,t), 4.26 (2H, q), 5.47 (1H, s), 6.97 (1H, m), 7.08 (1H, m), 7.55 (4H,m); IR: 2962, 2930, 2860, 1495, 1470, 1410, 1388, 1130, 1083, 1028, 812cm⁻¹ ; MS: 458 M!⁺, 316, 231.

EXAMPLE 67

2-(4"-Octyl-2",3"-difluorobiphenyl-4'-yl)-5-n-hexyl-1,3-dioxane

Quantities: compound from Example 12 (1.64 g, 5 mmol), compound fromExample 31 (1.42 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.1 g (47%); Purity (HPLC): 99.71%; Mesomorphism (T/°C.): K 63.8SmC 84.6 SmA 93.4 N 108.5 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, q), 1.12 (2H,q), 1.30 (18H, m), 1.64 (2H, q), 2.14 (1H, m), 2.68 (2H, t), 3.56 (2H,t), 4.25 (2H, q), 5.46 (1H, s), 6.96 (1H, m), 7.08 (1H, m), 7.54 (4H,m); IR: 2962, 2928, 2858, 1494, 1471, 1464, 1408, 1386, 1127, 1080,1026, 812 cm⁻¹ ; MS: 472 M!⁺, 330, 231.

EXAMPLE 68

2-(4"-Nonyl-2",3"-difluorobiphenyl-4'-yl)-5-n-hexyl-1,3-dioxane

Quantities: compound from Example 12 (1.64 g, 5 mmol), compound fromExample 32 (1.49 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 63.

Yield=1.7 g (70%); Purity (HPLC): 99.72%; Mesomorphism (T/°C.): K 62.0SmC 81.5 SmA 90.6 N 106.7 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, q), 1.11 (2H,q), 1.30 (20H, m), 1.64 (2H, q), 2.14 (1H, m), 2.68 (2H, t), 3.56 (2H,t), 4.25 (2H, q), 5.47 (1H, s), 6.97 (1H, m), 7.08 (1H, m), 7.55 (4H,m); IR: 2960, 2928, 2860, 1495, 1470, 1409, 1387, 1129, 1082, 1027, 812cm⁻¹ ; MS: 486 M!⁺, 344, 231.

EXAMPLE 69

2-(4"-Decyl-2",3"-difluorobiphenyl-4'-yl)-5-n-hexyl-1,3-dioxane

Quantities: compound from Example 12 (1.64 g, 5 mmol), compound fromExample 33 (1.63 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.2 g (48%); Purity (HPLC): 99.43%; Mesomorphism (T/°C.): K 68.7SmC 79.8 SmA 89.8 N 103.2 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, m), 1.12 (2H,q), 1.30 (22H, m), 1.64 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.57 (2H,t), 4.26 (2H, q), 5.47 (1H, s), 6.97 (1H, m), 7.08 (1H, m), 7.55 (4H,m); IR: 2960, 2930, 2858, 1495, 1471, 1467, 1408, 1387, 1129, 1082,1028, 812 cm⁻¹ ; MS: 500 M!⁺, 358, 231.

EXAMPLE 70

2-(4"-Pentoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-heptyl-1,3-dioxane

Quantities: compound from Example 13 (1.71 g, 5 mmol), compound fromExample 43 (1.34 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.3 g (56%); Purity (HPLC): 99.87%; Mesomorphism (T/°C.): K 58.5SmC 104.5 N 138.4 Iso; ¹ H NMR (CDCl₃): δ0.89 (3H, t), 0.94 (2H, t),1.11 (2H, q), 1.29 (12H, m), 1.85 (2H, q), 2.14 (1H, m), 3.55 (2H, t),4.07 (2H, t), 4.25 (2H, q), 5.46 (1H, s), 6.78 (1H, m), 7.07 (1H, m),7.53 (4H, m); IR: 2962, 2926, 2832, 1633, 1530, 1508, 1472, 1389, 1318,1303, 1292, 1083, 1065. 1022, 805 cm⁻¹ ; MS: 460 M!⁺, 389, 234.

EXAMPLE 71

2-(4"-Hexoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-heptyl-1,3-dioxane

Quantities: compound from Example 13 (1.71 g, 5 mmol), compound fromExample 44 (1.35 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.35 g (57%); Purity (HPLC): 99.72%; Mesomorphism (T/°C.): K 52.5SmC 102.1 N 135.5 Iso; ¹ H NMR (CDCl₃): δ0.91 (6H, q), 1.12 (2H, q),1.29 (12H, m), 1.35 (2H, m), 1.84 (2H, q), 2.14 (1H, m), 3.55 (2H, t),4.08 (2H, t), 4.25 (2H, q), 5.47 (1H, s), 6.74 (1H, m), 7.07 (1H, m),7.54 (4H, m); IR: 2964, 2934, 2860, 1630, 1528, 1508, 1471, 1388, 1316,1303, 1129, 1105, 1075, 1028, 806 cm⁻¹ ; MS: 474 M!⁺, 390, 234.

EXAMPLE 72

2-(4"¹¹ -Heptoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-heptyl-1,3-dioxane

Quantities: compound from Example 13 (1.72 g, 5 mmol), compound fromExample 45 (1.55 g, 5.7 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M. Theexperimental procedure was as described in Example 48.

Yield=1.2 g (49%); Purity (HPLC): 100.0%; Mesomorphism (T/°C.): K 58.7SmC 110.0 N 134.6 Iso; ¹ H NMR (CDCl₃): δ0.89 (6H, t), 1.11 (2H, q),1.30 (16H, m), 1.47 (2H, q), 1.84 (2H, q), 2.14 (1H, m), 3.57 (2H, t),4.07 (2H, t), 4.25 (2H, q), 5.46 (1H, s), 6.78 (1H, m), 7.07 (1H, m),7.53 (4H, m); IR: 2964, 2930, 2862, 1633, 1582, 1512, 1476, 1391, 1319,1305, 1137, 1087, 1026, 807 cm⁻¹ ; MS: 488 M!⁺, 389, 234.

EXAMPLE 73

2-(4"-Heptoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-heptyl-1,3-dioxane

Quantities: compound from Example 13 (1.71 g, 5 mmol), compound fromExample 46 (1.57 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.7 g (68%); Purity (HPLC): 99.56%; Mesomorphism (T/°C.): K 55.0SmC 102.6 N 129.4 Iso; ¹ H NMR (CDCl₃): δ0.91 (6H, m), 1.12 (2H, q),1.31 (18H, m), 1.48 (2H, q), 1.85 (2H, q), 2.15 (1H, m), 3.56 (2H, t),4.08 (2H, t), 4.26 (2H, q), 5.46 (1H, s), 6.78 (1H, m), 7.07 (1H, m),7.52 (4H, m); IR: 2960, 2928, 2858, 1626, 1530, 1509, 1473, 1410, 1387,1319, 1292, 1129, 1081, 1024, 800 cm⁻¹ ; MS: 502 M!⁺, 389, 234.

EXAMPLE 74

2-(4"-Heptoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-heptyl-1,3-dioxane

Quantities: compound from Example 13 (1.9 g, 5.5 mmol), compound fromExample 47 (1.5 g, 5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=0.66 g (26%); Purity (HPLC): 99.21%; Mesomorphism (T/°C.): K 56.9SmC 110.7 N 130.5 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, q), 1.11 (2H, q),1.33 (20H, m), 1.48 (2H, q), 1.83 (2H, q), 2.13 (1H, m), 3.58 (2H, t),4.07 (2H, t), 4.23 (2H, q), 5.46 (1H, s), 6.78 (1H, m), 7.07 (1H, m),7.54 (4H, m); IR: 2964, 2930, 2862, 1638, 1531, 1511, 1477, 1380, 1321,1298, 1138, 1080, 1029, 808 cm⁻¹ ; MS: 516 M!⁺, 389, 234.

EXAMPLE 75

2-(4"-Heptoxy-2",3"-difluoro-biphenyl-4'-yl)-5-n-heptyl-1,3-dioxane

Quantities: compound from Example 13 (1.71 g, 5 mmol), compound fromExample 28 (1.20 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.5 g (68%); Purity (HPLC): 100.0%; Mesomorphism (T/°C.): K 60.0SmC 88.0 SmA 106.2 N 121.2 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, q), 1.12(2H, q), 1.30 (12H, m), 1.36 (2H, m), 1.64 (2H, q), 2.15 (1H, m), 2.69(2H, t), 3.57 (2H, t), 4.26 (2H, q), 5.47 (1H, s), 6.97 (1H, m), 7.08(1H, m), 7.56 (4H, m); IR: 2968, 2934, 2860, 1492, 1467, 1404, 1385,1127, 1086, 1023, 813 cm⁻¹ ; MS: 444 M!⁺, 288, 231.

EXAMPLE 76

2-(4"-Heptoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-heptyl-1,3-dioxane

Quantities: compound from Example 13 (1.71 g, 5 mmol), compound fromExample 29 (1.33 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.4 g (61%); Purity (HPLC): 99.69%; Mesomorphism (T/°C.): K 62.5SmA 105.2 N 111.2 Iso; ¹ H NMR (CDCl₃): δ0.91 (6H, q), 1.11 (2H, q),1.30 (16H, m), 1.64 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.55 (2H, t),4.25 (2H, q), 5.46 (1H, s), 6.96 (1H, m), 7.07 (1H, m), 7.53 (4H, m);IR: 2962, 2934, 2860, 1493, 1464, 1408, 1387, 1129, 1082, 1025, 811 cm⁻¹; MS: 458 M!⁺, 302, 231.

EXAMPLE 77

2-(4"-Heptoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-heptyl-1,3-dioxane

Quantities: compound from Example 13 (1.71 g, 5 mmol), compound fromExample 30 (1.34 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.3 g (55%); Purity (HPLC): 99.77%; Mesomorphism (T/°C.): K 63.5SmC 68.5 SmA 106.0 N 114.2 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, t), 1.12(2H, q), 1.30 (18H, m), 1.64 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.57(2H, t), 4.26 (2H, q), 5.47 (1H, s), 6.97 (1H, m), 7.08 (1H, m), 7.55(4H, m); IR: 2962, 2930, 2862, 1470, 1410, 1388, 1129, 1082, 1026, 813cm⁻¹ ; MS: 472 M!⁺, 316, 231.

EXAMPLE 78

2-(4"-Heptoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-heptyl-1,3-dioxane

Quantities: compound from Example 13 (1.71 g, 5 mmol), compound fromExample 31 (1.49 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.6 g (66%); Purity (HPLC): 99.67%; Mesomorphism (T/°C.): K 64.5SmA N 105.9 N 110.8 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, m), 1.12 (2H, q),1.30 (20H, m), 1.64 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.56 (2H, t),4.25 (2H, q), 5.46 (1H,s), 6.96 (1H, m), 7.07 (1H, m), 7.53 (4H, m); IR:2960, 2930, 2858, 1494, 1470, 1408, 1387, 1128, 1081, 1025, 812 cm⁻¹ ;MS: 486 M!⁺, 330, 231.

EXAMPLE 79

2-(4"-Heptoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-heptyl-1,3-dioxane

Quantities: compound from Example 13 (1.75 g, 5 mmol), compound fromExample 32 (1.49 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(174 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.65 g (66%); Purity (HPLC): 100.0%; Mesomorphism (T/°C.): K 71.5SmC 86.7 SmA 106.2 N 112.6 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, m), 1.12(2H, q), 1.30 (22H, m), 1.65 (2H, q), 2.15 (1H, m), 2.69 (2H, t), 3.56(2H, t), 4.25 (2H, q), 5.48 (1H, s) 6.97 (1H, m), 7.07 (1H, m), 7.53(4H, m); IR: 2962, 2932, 2860, 1495, 1470, 1408, 1387, 1129, 1082, 1026,813 cm⁻¹ ; MS: 500 M!⁺, 344, 231.

EXAMPLE 80

2-(4"-Heptoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-heptyl-1,3-dioxane

Quantities: compound from Example 13 (1.71 g, 5 mmol), compound fromExample 33 (1.63 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.98 (74%); Purity (HPLC): 99.76%; Mesomorphism (T/°C.): K 66.0SmA 104.1 N 107.8 Iso; ¹ H NMR (CDCl₃): δ0.89 (6H, q), 1.11 (2H, q),1.30 (24H, m), 1.64 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.57 (2H, t),4.26 (2H, q), 5.48 (1H, s), 6.97 (1H, m), 7.08 (1H, m), 7.55 (4H, m);IR: 2960, 2930, 2860, 1493, 1470, 1405, 1386, 1128, 1081, 1025, 811 cm⁻¹; MS: 514 M!⁺, 359, 231.

EXAMPLE 81

2-(4"-Heptoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-octyl-1,3-dioxane

Quantities: compound from Example 14 (1.80 g, 5 mmol), compound fromExample 43 (1.28 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.58 (63%); Purity (HPLC): 100.0%; Mesomorphism (T/°C.): K 56.0SmC 112.5 N 134.1 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, sex), 1.12 (2H, m),1.30 (14H, m), 1.45 (2H, q), 1.84 (2H, q), 2.15 (1H, m), 3.56 (2H, t),4.08 (2H, t), 4.26 (2H, q), 5.46 ()1H, s), 6.79 (1H, m), 7.07 (1H, m),7.53 (4H, m); IR: 2962, 2928, 2858, 1633, 1504, 1472, 1406, 1395, 1317,1290, 1132, 1105, 1078, 1025, 800 cm⁻¹ ; MS: 474 M!⁺, 404, 234.

EXAMPLE 82

2-(4"-Heptoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-octyl-1,3-dioxane

Quantities: compound from Example 14 (1.80 g, 5 mmol), compound fromExample 44 (1.35 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.75 g (72%); Purity (HPLC): 99.74%; Mesomorphism (T/°C.): K 51.5SmC 102.5 SmA 108.0N 130.2 Iso; ¹ H NMR (CDCl₃): δ0.91 (6H, q), 1.12(2H, q), 1.29 (14H, m), 1.35 (2H, m), 1.48 (2H, q), 1.85 (2H, q), 2.15(1H, m), 3.56 (2H, t), 4.08 (2H, t) 4.26 (2H, q), 5.47 (1H, s), 6.79(1H, m), 7.08 (1H, m), 7.55 (4H, m); IR: 2962, 2936, 2860, 1630, 1507,1473, 1412, 1387, 1320, 1302, 1193, 1129, 1082, 1023, 800 cm⁻¹ ; MS: 488M!⁺, 403, 234.

EXAMPLE 83

2-(4"-Heptoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-octyl-1,3-dioxane

Quantities: compound from Example 14 (1.80 g, 5 mmol), compound fromExample 45 (1.43 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.85 g (74%); Purity (HPLC): 99.67%; Mesomorphism (T/°C.): K 57.0SmC 101.4 SmA 109.2N 122.8 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, m), 1.12(2H, q), 1.29 (18H, m), 1.48 (2H, q), 1.85 (2H, q), 2.15 (1H, m), 3.56(2H, t), 4.08 (2H, t), 4.26 (2H, q), 5.47 (1H, s), 6.78 (1H, m), 7.07(1H, m), 7.55 (4H, m); IR: 2962, 2932, 2860, 1632, 1509, 1470, 1404,1385, 1318, 1293, 1133, 1078, 1028, 824, 804 cm⁻¹ ; MS: 502 M!⁺, 403,234.

EXAMPLE 84

2-(4"-Octoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-octyl-1,3-dioxane

Quantities: compound from Example 14 (1.78 g, 5 mmol), compound fromExample 46 (1.50 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.8 g (70%); Purity (HPLC): 100.0%; Mesomorphism (T/°C.): K 50.5SmC 97.1 SmA 107.7N 120.2 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, t), 1.12 (2H,q), 1.30 (20H, m), 1.48 (2H, q), 1.84 (2H, q), 2.14 (1H, m), 3.55 (2H,t), 4.07 (2H, t), 4.25 (2H, q), 5.47 (1H, s), 6.78 (1H, m), 7.07 (1H,m), 7.53 (4H, m); IR: 2960, 2930, 2858, 1633, 1508, 1474, 1386, 1317,1292, 1133, 1087, 1028. 802 cm⁻¹ ; MS: 516 M!⁺, 403, 234.

EXAMPLE 85

2-(4"-Nonoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-octyl-1,3-dioxane

Quantities: compound from Example 14 (1.78 g, 5 mmol), compound fromExample 47 (1.57 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.3 g (49%); Purity (HPLC): 99.63%; Mesomorphism (T/°C.): K 67.0SmC 115.4N 127.6 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, t), 1.12 (2H, q), 1.30(24H, m), 1.85 (2H, q), 2.15 (1H, m), 3.55 (2H, t), 4.07 (2H, t), 4.25(2H, q), 5.46 (1H, s), 6.78 (1H, m), 7.07 (1H, m), 7.53 (4H, m); IR:2932, 2858, 1635, 1508, 1474, 1404, 1387, 1318, 1298, 1133, 1077, 1028,803 cm⁻¹ ; MS: 530 M!⁺, 403, 234.

EXAMPLE 86

2-(4"-Pentyl-2",3"-difluorobiphenyl-4'-yl)-5-n-octyl-1,3-dioxane

Quantities: compound from Example 13 (1.80 g, 5 mmol), compound fromExample 28 (1.20 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.6 g (70%); Purity (HPLC): 99.82%; Mesomorphism (T/°C.): K 57 SmC82.2 SmA 109.8N 115.1 Iso; ¹ H NMR (CDCl₃): δ0.91 (6H, q), 1.12(2H, q),1.30 (14H, m), 1.36 (2H, m), 1.64 (2H, q), 2.15 (1H, m), 2.69 (2H, t),3.57 (2H, t), 4.25 (2H, q) 5.48 (1H, s), 6.97 (1H, m), 7.08 (1H, m),7.55 (4H, m); IR: 2962, 2934, 2862, 1494, 1470, 1408, 1388, 1130, 1082,1026, 812 cm⁻¹ ; MS: 458 M!⁺, 288, 231.

EXAMPLE 87

2-(4"-hexyl-2",3"-difluorobiphenyl-4'-yl)-5-n-octyl-1,3-dioxane

Quantities: compound from Example 13 (1.78 g, 5 mmol), compound fromExample 29 (1.30 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.4 g (54%); Purity (HPLC): 99.55%; Mesomorphism (T/°C.): K 60.8SmC 97.2 SmA 110.9N 113.5 Iso; ¹ H NMR (CDCl₃): δ0.89 (6H, q), 1.11 (2H,q), 1.29 (18H, m), 1.64 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.56 (2H,t), 4.25 (2H, q), 5.46 (1H, s), 6.96 (1H, m), 7.07 (1H, m), 7.54 (4H,m); IR: 2962, 2934, 2862, 1493, 1467, 1407, 1388, 1129, 1083, 1027, 813cm⁻¹ ; MS: 472 M!⁺, 302, 231.

EXAMPLE 88

2-(4"-Heptyl-2",3"-difluorobiphenyl-4'-yl)-5-n-octyl-1,3-dioxane

Quantities: compound from Example 14 (2.04 g, 5.74 mmol), compound fromExample 30 (1.60 g, 6.24 mmol), tetrakis(triphenylphosphine)palladium(0)(190 mg, 0.165 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48 Yield=1.3 g (47%);Purity (HPLC): 99.72%; Mesomorphism (T/°C.): K 66.0 SmC 98.3 SmA 109.5N113.7 Iso; ¹ H NMR (CDCl₃): δ0.89 (6H, t), 1.11 (2H, q), 1.29 (20H, m),1.64 (2H, q), 2.14 (1H, m), 2.68 (2H, t), 3.55 (2H, t), 4.25 (2H, q),5.45 (1H, s), 6.97 (1H, m), 7.07 (1H, m), 7.55 (4H, m); IR: 2960, 2932,2860, 1493, 1470, 1407, 1387, 1129, 1081, 1025, 811 cm⁻¹ ; MS: 486 M!⁺,316, 231.

EXAMPLE 89

2-(4"Octyl-2", 3"-difluorobiphenyl-4'-yl )-5-n-octyl-1,3-dioxane

Quantities: compound from Example 14 (1.80 g, 5 mmol), compound fromExample 31 (1.42 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0. 15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.7 g (68%); Purity (HPLC): 99.83%; Mesomorphism (T/°C.): K 66.5SmC 94.0 SmA 109.3N 110.9 Iso: ¹ H NMR (CDCl₃): δ0.90 (6H, q), 1.11 (2H,q), 1.30 (22H, m), 1.64 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.55 (2H,t), 4.25 (2H, q), 5.46 (1H, s), 6.96 (1H, m), 7.07 (1H, m), 7.53 (4H,m): IR: 2960, 2930, 2858, 1493, 1470, 1407, 1386, 1129, 1081, 1024, 811cm⁻¹ ; MS: 500 M!⁺, 330, 231.

EXAMPLE 90

2-(4"-Nonyl-2",3"-difluorobiphenyl-4'-yl)-5-n-octyl-1,3-dioxane

Quantities: compound from Example 14 (1.78 g, 5 mmol), compound fromExample 32 (1.49 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.6 g (62%); Purity (HPLC): 99.83%; Mesomorphism (T/°C.): K 67.4SmC 95.0 SmA 108.6N 110.8 Iso; ¹ H NMR (CDCl₃): δ 0.90 (6H, q), 1.12(2H, q), 1.31 (24H, m), 1.64 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.56(2H, t), 4.25 (2H, q), 5.47 (1H, s), 6.97 (1H, m), 7.08 (1H, m), 7.55(4H, m); IR: 2960, 2928, 2858, 1494, 1470, 1407, 1387, 1128, 1081, 1025,802 cm⁻¹ ; MS: 514 M!⁺, 344, 231.

EXAMPLE 91

2-(4"-Decyl-2",3"-difluorobiphenyl-4'-yl)-5-n-octyl-1,3-dioxane

Quantities: compound from Example 14 (1.78 g, 5 mmol), compound fromExample 33 (1.57 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0. 15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.7 g (64%); Purity (HPLC): 99.74%; Mesomorphism (T/°C.): K 68.0SmC 90.1 SmA 106.8N 107.5 Iso; ¹ H NMR (CDCl₃): δ0.91 (6H, q), 1.12 (2H,q), 1.32 (26H, m), 1.65 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.55 (2H,t), 4.26 (2H, q), 5.46 (1H, s), 6.97 (1H, m), 7.07 (1H, m), 7.55 (4H,m); IR: 2962, 2930, 2860. 1494, 1474, 1406, 1387, 1129, 1082, 1027, 812cm⁻¹ ; MS: 528 M!⁺, 358, 231.

EXAMPLE 92

2-(4"Pentoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-oyl-1,3-dioxane

Quantities: compound from Example 15 (1.85 g, 5 mmol), compound fromExample 43 (1.28 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.45 g (59%); Purity (HPLC): 99.57%; Mesomorphism (T/°C.): K 54.5SmB 55.8 SmC 111.5 SmA 118.0N 130.8 Iso: ¹ H NMR (CDCl₃): δ0.92 (6H, m),1.12 (2H, q), 1.30 (16H, ml, 1.45 (2H, m), 1.86 (2H, q), 2.15 (1H, m),3.56 (2H, t), 4.07 (2H, t), 4.25 (2H, q), 5.47 (1H, s), 6.78 (1H, m),7.07 (1H, m), 7.53 (4H, m); IR: 2958, 2922, 2844, 1633, 1505, 1468,1383, 1301, 1128, 1072, 821, 793 cm⁻¹ ; MS: 516 M!⁺, 417, 234.

EXAMPLE 93

2-(4"-Hexoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-nonyl-1,3-dioxane

Quantities: compound from Example 15 (1.85 g, 5 mmol), compound fromExample 44 (1.35 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=0.65 g (26%); Purity (HPLC): 99.40%; Mesomorphism (T/°C.): K 54.0SmC 121.1N 136.0 Iso; ¹ H NMR (CDCl₃): δ0.92 (6H, q), 1.12 (2H, q), 1.30(16H, m), 1.36 (2H, m), 1.45 (2H, m), 1.84 (2H, q), 2.15 (1H, m), 3.56(2H, t), 4.08 (2H, t,), 4.26 (2H, q), 5.47 (1H, s), 6.78 (1H, m), 7.07(1H, m), 7.53 (4H, m); IR: 2960, 2936, 2862, 1638, 1509, 1478, 1397,1320, 1304, 1295, 1135, 1108, 1080, 1029, 801 cm⁻¹ ; MS: 502 M!⁺, 417,234.

EXAMPLE 94

2-(4"-Heptoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-nonyl-1,3-dioxane

Quantities: compound from Example 15 (1.85 g, 5 mmol), compound fromExample 45 (1.55 g, 5.7 mmol ), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.4 g (54%); Purity (HPLC): 99.76%; Mesomorphism (T/°C.): K 54.0SmC 121.7N 132.3 Iso: ¹ H NMR (CDCl₃): δ0.89 (6H, sex), 1.11 (2H, q),1.27 (22H, m), 1.84 (2H, q), 2.14 (1H, m), 3.57 (2H, t), 4.07 (2H, t),4.25 (2H, m), 5.45 (1H, s), 6.78 (1H, m), 7.07 (1H, m), 7.58 (4H, m);IR: 2958, 2932, 2850, 1635, 1530, 1510, 1470, 1385, 1318, 1293, 1133,1077, 1028, 803 cm⁻¹ ; MS: 516 M!⁺, 417, 234.

EXAMPLE 95

2-(4"-Octoxy-2",3"-difluorobiphenyl-4'-yl)-5-n-nonyl-1,3-dioxane

Quantities: compound from Example 15 (1.85 g, 5 mmol), compound fromExample 46 (1.5 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(174 mg, 0. 15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.9 g (72%); Purity (HPLC): 99.52%; Mesomorphism (T/°C.): K 43.4SmC 110.2 SmA 118.4N 127.7 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, t), 1.12(2H, q), 1.30 (22H, m), 1.45 (2H, q), 1.84 (2H, q), 2.15 (1H, m), 3.57(2H, t), 4.08 (2H, t), 4.25 (2H, q), 5.47 (1H, s), 6.79 (1H, m), 7.08(1H, m), 7.54 (4H, m); IR: 2958, 2920, 2848, 1633, 1505, 1468, 1383,1300, 1128, 1070, 1020, 791 cm⁻¹ ; MS: 530 M!⁺, 417, 234.

EXAMPLE 96

2-(4"-Nonoxy-2",3"-difluorobiphenyl-4'-y 1)-5-n-nonyl-1,3-dioxane

Quantities: compound from Example 15 (2.03 g, 5.5 mmol), compound fromExample 47 (1.6 g, 5 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.4 g (51%); Purity (HPLC): 99.63%; Mesomorphism (T/°C.): K 61.1SmC 122.3N 129.7 Iso; ¹ H NMR (CDCl₃): δ0.89 (6H, t), 1.10 (2H, q), 1.29(24H, m), 1.47 (2H, q), 1.84 (2H, q), 2.14 (1H, m), 3.56 (2H, t), 4.06(2H, t), 4.25 (2H, q), 5.45 (1H, s) 6.78 (1H, m), 7.07 (1H, m), 7.53(4H, m); IR: 2962, 2934, 2860, 1638, 1582, 1512, 1475, 1389, 1322, 1137,1080, 1031, 808 cm⁻¹ ; MS: 544 M!⁺, 417, 234.

EXAMPLE 97

2-(4"-Pentyl-2",3"-difluorobiphenyl-4'-yl)-5-n-nonyl-1,3-dioxane

Quantities: compound from Example 15 (1.85 g, 5 mmol), compound fromExample 28 (1.2 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.6 g (68%): Purity (HPLC): 99.55%; Mesomorphism (T/°C.): K 58 SmC84.7 SmA 114.3N 115.8 Iso: ¹ H NMR (CDCl₃): δ0.90 (6H, q), 1.11 (2H, q),1.27 (16H, m), 1.35 (2H, q), 1.64 (2H, q), 2.15 (1H, m), 2.69 (2H, t),3.56 (2H, t), 4.26 (2H, q), 5.49 (1H, s), 6.97 (1H, m), 7.08 (1H, m),7.58 (4H, m); IR: 2960, 2930, 2852, 1497, 1469, 1410, 1386, 1168, 1131,1083, 1026, 810 cm⁻¹ ; MS: 472 M!⁺, 288, 231.

EXAMPLE 98

2-(4"-Hexyl-2",3"-difluorobiphenyl-4'-yl)-5-n-nonyl-1,3-dioxane

Quantities: compound from Example 15 (1.85 g, 5 mmol), compound fromExample 29 (1.27 g, 5.25mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 63.

Yield=0.4 g (16%); Purity (HPLC): 99.58%; Mesomorphism (T/°C.): K 57.5SmC 99.3N 113.4 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, m), 1.12 (2H, q), 1.29(20H, m), 1.64 (2H, q), 2.15 (1H, m), 2.69 (2H, t), 3.57 (2H, t), 4.26(2H, t), 5.47 (1H, s), 6.97 (1H, m), 7.08 (1H, m), 7.55 (4H, m); IR:2962, 2930, 2860, 1493, 1469, 1407, 1386, 1129, 1081, 1025, 811 cm⁻¹ ;MS: 486 M!⁺, 302, 231.

EXAMPLE 99

2-(4"-Heptyl-2",3"-difluorobiphenyl-4'-yl)-5-n-nonyl-1,3-dioxane

Quantities: compound from Example 15 (1.85 g, 5 mmol), compound fromExample 30 (1.34 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 63.

Yield=1.6 g (64%); Purity (HPLC): 100.0%; Mesomorphism (T/°C.): K 61.4SmC 93.3 SmA 113.2N 113.5 Iso: ¹ H NMR (CDCl₃): δ0.90(6H, q), 1.11 (2H,q), 1.30 (22H, m), 1.64 (2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.56 (2H,t), 4.26 (2H, q), 5.46 (1H, s), 6.96 (1H, m), 7.07 (1H, m), 7.54 (4H,m); IR: 2962, 2932, 2860, 1496, 1470, 1408, 1387, 1130, 1083, 1027, 812cm⁻¹ ; MS: 500 M!⁺, 316, 231.

EXAMPLE 100

2-(4"-Octyl-2",3"-difluorobiphenyl-4'-yl)-5-n-nonyl-1,3-dioxane

Quantities: compound from Example 15 (1.85 g, 5 mmol), compound fromExample 31 (1.42 g, 5.25mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 63.

Yield=1.95 g (76%); Purity (HPLC): 99.45%; Mesomorphism (T/°C.): K 64.0SmC 97.3 SmA 113.0 Iso; ¹ H NMR (CDCl₃): δ0.90(6H, q), 1.12 (2H, q),1.30 (24H, m), 1.64 (2H, q), 2.15 (1H, m), 2.69 (2H, t), 3.56 (2H, t),4.25 (2H, q), 5.45 (1H, s), 6.96 (1H, m), 7.07 (1H, m), 7.53 (4H, m);IR: 2962, 2930, 2858, 1495, 1470, 1408, 1387, 1130, 1083, 1026, 812 cm⁻¹; MS: 514 M!⁺, 330, 231.

EXAMPLE 101

2-(4"-Nonyl-2",3"-difluorobiphenyl-4'-yl)-5-n-nonyl-1,3-dioxane

Quantities: compound from Example 15 (1.85 g, 5 mmol), compound fromExample 32 (1.49 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 63.

Yield=2.0 g (76%); Purity (HPLC): 99.58%; Mesomorphism (T/°C.): K 69.0SmC 98.2 SmA 112.2 Iso; ¹ H NMR (CDCl₃): δ0.90(6H, q), 1.11 (2H, q),1.30(26H, m), 1.64 (2H, q), 2.15 (1H, m), 2.69 (2H, t), 3.57 (2H, t),4.26 (2H, q), 5.46 (1H, s), 6.96 (1H, m), 7.07 (1H, m), 7.53 (4H, m);IR: 2962, 2932, 2860, 1496, 1470, 1409, 1388, 1130, 1083, 1027, 813 cm⁻¹; MS: 528 M!⁺, 344, 231.

EXAMPLE 102

2-(4"-Decyl-2",3"-difluorobiphenyl-4'-yl)-5-n-nonyl-1,3-dioxane

Quantities: compound from Example 15 (1.85 g, 5 mmol), compound fromExample 33 (1.57 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(173 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 63.

Yield=2.2 g (81%); Purity (HPLC): 99.66%; Mesomorphism (T/°C.): K 68.0SmC 95.1 SmA 111.1 Iso: ¹ H NMR (CDCl₃): δ0.90(6H, q), 1.12 (2H, q),1.30 (28H, m), 1.64(2H, q), 2.15 (1H, m), 2.68 (2H, t), 3.56 (2H, t),4.26 (2H, q), 5.46 (1H, s), 6.97 (1H, m), 7.08 (1H, m), 7.55 (4H, m);IR: 2962, 2932, 2860, 1496, 1470, 1407, 1387, 1129, 1082, 1027, 812 cm⁻¹; MS: 542 M!⁺, 358, 231.

EXAMPLE 103

2-4"-(2-Methylhexoxy)-2",3"-difluorobiphenyl-4'-yl!-5-n-nonyl-1,3-dioxane

Quantities: compound from Example 15 (1.85 g, 5 mmol), compound fromExample 35 (1.43 g, 5.25 mmol), tetrakis(triphenylphosphine)palladium(0)(175 mg, 0.15 mmol) and aqueous sodium carbonate (5 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=1.7 g (66%); Purity (HPLC): 99.56%; Mesomorphism (T/°C.): K 57.0SmA 100.4 Iso; ¹ H NMR (CDCl₃): δ0.91 (6H, m), 1.05 (3H, d), 1.11 (2H,q), 1.28 (20H, m), 1.99 (1H, m), 2.14 (1H, m), 3.55 (2H, t), 3.83 (1H,q), 3.93 (1H, q), 4.25 (2H, t), 5.45 (1H, s), 6.78 (1H, m), 7.07 (1H,m), 7.53 (4H, m); IR: 2954, 2922, 2854, 1637, 1503, 1466, 1392, 1315,1288, 1132, 1077, 1024, 798 cm⁻¹ ; MS: 516 M!⁺, 417, 234.

EXAMPLE 104

4-(5'-n-Pentyl-1',3'-dioxan-2'-yl) benzoic acid (Formula 13)

A solution of n-butyllithium (3 cm³, 10.0M in hexanes, 30 mmol) wasadded dropwise to a stirred, cooled (-78° C.) solution of compound fromExample 11 (9.4 g, 30 mmol) in dry THF (100 cm³) under an atmosphere ofdry nitrogen. The mixture was maintained under these conditions (35 min)then poured onto carbon dioxide granules. The product was extracted into10% sodium hydroxide (2×150 cm³) and the combined basic exacts acidifiedwith hydrochloric acid (36%). The product was extracted into a mixtureof diethyl ether and THF (3:1, 2×150 cm³) and dried (MgSO₄). The solventwas removed in vacuo to yield a colourless solid.

Yield=7.8 g (93%); m.p.=206°-208° C.; ¹ H NMR (CDCl₃): δ0.90 (3H, t),1.11 (2H, q), 1.30 (6H, m), 2.12 (1H, m), 3.55 (2H, t), 4.24 (2H, q),5.45 (1H, s), 7.54 (2H, m), 8.04 (2H, m); IR: 3200-2500, 2970, 2936,2868, 1712, 1697, 1615, 1580, 1470, 1427, 1385, 1288, 1130, 1082, 1020,845, 765 cm⁻¹ ; MS: 278 M!⁺, 151.

EXAMPLE 105

4-(5'-n-Nonyl-1',3'-dioxan-2'-yl) benzoic acid

Quantities: n-butyllithium (2 cm³, 10.0M in hexanes, 20 mmol), compoundfrom Example 15 (7.4 g, 20 mmol). The experimental procedure was asdescribed in Example 104.

Yield=5.0 g (75%); m.p.=197°-198° C.; ¹ H NMR (CDCl₃): δ0.89 (3H, t),1.11 (2H, q), 1.27 (14H, m), 2.14 (1H, m), 3.55 (2H, t), 4.26 (2H, q),5.46 (1H, s), 7.60 (2H, m), 8.10 (2H, m); IR: 3200-2500, 2964, 2930,2856, 1682, 1430, 1387, 1293, 1130, 1087, 1023, 846, 763 cm⁻¹ ; MS: 334M!⁺, 333, 214.

EXAMPLE 106

4-n-Nonyl-2,3-difluorophenol (Formula 14)

Quantities: compound from Example 32 (13.6 g, 60 mmol) and H₂ O₂, (10%,61 cm³). The experimental procedure was described in Example 37.

Yield=12.6 g (98%); m.p.=29°-31° C.; ¹ H NMR (CDCl₃): δ0.88 (3H, t),1.27 (12H, m), 1.57 (2H, m), 2.56 (2H, t), 4.98 (1H, d), 6.65-6.83 (2H,m); IR: 3600-3100, 2930, 2860, 1645, 1513, 1487, 1310, 1180, 1027, 821cm⁻¹ ; MS: 256 M!⁺, 143.

EXAMPLE 107

4-n-Penyl-2,3-difluorophenol

Quantities: compound from Example 28 (13.6 g, 60 mmol) and H₂ O₂ (10%,61 cm³). The experimental procedure was as described previously inExample 37.

Yield=11.2 g (93%); ¹ H NMR (CDCl₃): δ0.89 (3H, t), 1.32 (4H, m), 1.57(2H, q), 2.57 (2H, t), 5.02 (1H, d), 6.69 (1H, m), 6.80 (1H, m): IR:3600-3100, 2960, 2930, 2864, 1646, 1608, 1513, 1490, 1309, 1182, 1037,812 cm⁻¹ ; MS: 200 M!⁺, 143.

EXAMPLE 108

4"-n-Nonyl-2",3"-difluorophenyl 4-(5-n-pentyl-1',3'-dioxan-2'-yl)benzoate (Formula 15)

A mixture of compound from Example 104 (1.28 g, 5 mmol), compound fromExample 106 (1.39 g, 5 mmol), N,N'-dicyclohexylcarbodiimide (1.03 g, 5mmol) and 4-(N,N'-dimethylamino)pyridine (0.06 g, 0.5 mmol) insodium-dried diethyl ether (90 cm³) and dry THF (60 cm³) was stirredovernight at room temperature. The reaction mixture was filtered and thefiltrate washed with water (2×25 cm³) and dried (MgSO₄). The solvent wasremoved in vacuo and the product was purified by flash columnchromatography (dichloromethane) and recrystallised from methanol/lightpetrol (1:1) to give colourless crystals.

Yield=0.85 g (33%); Purity (HPLC): 100.0%; Mesomorphism: (T/°C.) K 59SmA 82 125.2 Iso (SmA-SmC 40); ¹ H NMR (CDCl₃): δ0.89 (6H, sex), 1.12(2H, m), 1.29 (18H, m), 1.62 (2H, m), 2.15 (1H, m), 2.66 (2H, t), 3.56(2H, t), 4.27 (2H, q), 5.49 (1H, s), 6.96 (2H, d), 7.64 (2H, d), 8.20(2H, d); IR: 2928, 2856, 1753, 1503, 1485, 1470, 1272, 1250, 1128, 1073,1030, 1020, 758 cm⁻¹ ; MS: 516 M!⁺, 471, 389, 261.

EXAMPLE 109

4"-n-Pentyl-2",3"-difluorophenyl 4-(5 '-n-nonyl-1',3'-dioxan-2'-yl)benzoate

Quantities: compound from Example 105 (1g, 5 mmol), compound fromExample 107 (1.67 g, 5 mmol), N,N'-dicyclohexylcarbodiimide (1.03 g, 5mmol), 4-(N,N'-dimethylamino)pyridine (0.06 g, 0.5 mmol). Theexperimental procedure was described in Example 108.

Yield=0.9 g (35%); Purity (HPLC): 100.0%; Mesomorphism: (T/°C.) K 65.9SmA 115.9 130.1 Iso (SmA-SmC 70.3); ¹ H NMR (CDCl₃): δ0.90 (6H, sex),1.11 (2H, q), 1.28 (16H, m), 1.34 (2H, q), 1.63 (2H, q), 2.15 (1H, m),2.66 (2H, sex), 3.56 (2H, t), 4.27 (2H, q), 5.50 (1H, s), 6.96 (2H, d),7.64 (2H, d), 8.20 (2H, sex); IR: 2960, 2928, 2862, 1741, 1500, 1490,1470, 13.85, 1266, 1247, 1166, 1111, 1085, 1025, 812 cm⁻¹ ; MS: 516 M!⁺,317.

EXAMPLE 110

4'-Bromo-2,3-difluoro-4-nonoxybiphenyl (Formula 17)

Quantities: tetrakis(triphenylphosphine)palladium(0) (0.87 g, 0.75mmol), compound from Example 47 (9 g, 30 mmol) and 1-bromo-4-iodobenzene(7.07 g, 25 mmol). The experimental procedure was as described inExample 48 except that the reaction was carried out under conditions ofreflux (5 h). The crude product was purified by flash columnchromatography (light petrol/dichloro methane, 5:1) to give a colourlesssolid (9 g) which was recrystallised from light petrol to yieldcolourless crystals.

Yield=5.8 g (56%); m.p.=46°-47.5° C.; ¹ H NMR (CDCl₃): δ0.89 (3H, t),1.28 (12H, m), 1.85 (2H, q), 4.07 (2H, t), 6.79 (1H, m), 7.06 (1H, m),7.37 (2H, m), 7.56 (2H, m); IR: 2922, 2852, 1640, 1527, 1500, 1470,1396, 1317, 1302, 1200, 1112, 1103, 1082, 1075, 804 cm⁻¹ ; MS: 412 M!+,410 M!⁺, 286, 284.

EXAMPLE 111

(2',3'-Difluoro-4'-n-nonoxybiphen-4'-yl) boronic acid (Formula 18)

Quantities: compound from Example 110 (2.8 g, 6.8 mmol), n-butyllithium(4.4 cm³, 1.55M in hexanes, 6.8 mmol) and triisopropyl borate (2.6 g,13.8mmol). The experimental procedure was as described in Example 36.

Yield=2.6 g (100%); ¹ H NMR (CDCl₃): δ0.89 (3H, m), 1.29 (12H, m), 1.87(2H, m), 2,32 (2H, band), 4.10 (2H, m), 6.83 (1H, m), 7.15 (1H, m),7.34-7.58 (1H, m), 7.67 (1H, q), 7.81 (1H, d), 8.33 (1H, d) ;IR:3700-3000, 2960, 2924, 2856, 1613, 1516, 1470, 1402, 1198, 1082, 803cm⁻¹ ; MS: 332 M-B(OH)₂ !⁺, 206.

EXAMPLE 112

1-(2",3"-Difluoro-4"-n-nonoxy-4'-biphenyl)-4-n-heptyl-2,6-dioxaborinane(Formula 19)

Quantities: compound from Example 111 (1.9 g, 5 mmol) and compound fromExample 8 (0.9 g, 5 mmol). The experimental procedure was as describedin Example 11 except the product purified by flash column chromatography(dichloromethane/light petrol: 1:1) and recrystallisation from a mixtureof light petrol/methanol (3:1),

Yield=1.4 g (54 % ); Purity (HPLC): 99.75%; Mesomorphism: (T/°C.) K 72.5SmC 81.5N N 109.5 Iso; ¹ H NMR (CDCl₃): δ0.89 (6H, t), 1.29 (24H, m),1.85 (2H, q), 2.10 (1H, m), 3.78 (2H, t), 4.07 (2H, t), 4.19 (2H, q),6.79 (1H, m), 7.11 (1H, m), 7.49 (2H, m), 7.83 (2H, m); IR: 2940, 2872,1617, 1533, 1513, 1486, 1478, 1432, 1355, 1322, 1305, 1255, 1088, 816cm⁻¹ ; MS: 514 M!⁺, 388, 232.

EXAMPLE 113

1-(2",3"-Difluoro-4"n-nonoxy-4'biphenyl)-4-n-heptyl-2,6-dioxaborinane

Quantities: compound from Example 111 (1.9 g, 5 mmol) and compound fromExample 10 (0.9 g, 5 mmol). The experimental procedure was as describedin Example 112.

Yield=1.6 g (59 %); Purity (HPLC): 99.58%; Mesomorphism: CT/°C.) K 55.5SmC 103.5N N 111.3 Iso; ¹ H NMR (CDCl₃): δ0.88 (6H, t), 1.28 (26H, m),1.48 (2H, q), 1.84 (2H, q), 2.08 (1H, m), 3.78 (2H, t), 4.07 (2H, t),4.19 (2H, q), 6.79 (1H, m), 7.10 (1H, m), 7.49 (2H, q), 7.83 (2H, d);IR: 2960, 2912, 2858, 1630, 1606, 1524, 1465, 1345, 1312, 1069, 890, 835cm⁻¹ ; MS: 542 M!⁺, 415, 231.

EXAMPLE 114

2-(2',3'-Difluorophenyl)-5-n-heptyl-1,3-dioxane (Formula 18)

Quantities: compound from Example 8 (27 g, 0.155 mol),2,3-difluorobenzaldehyde (21.5 g, 0.15 mol) and 4-toluenesulphonic acid(100 mg). The experimental procedure was as described in Example 11except using dry benzene instead of dry toluene.

Yield=12.6 g (28%); m.p.=20°-21° C.; ¹ H NMR (CDCl₃): δ0.89 (3H, t),1.10 (2H, q), 1.28 (10H, m), 2.15 (1H, m), 3.56 (2H, t), 4.23 (2H, q),5.75 (1H, s), 7.11 (2H, m), 7.38 (1H, m); IR: 2974, 2944, 2870, 1641,1610, 1500, 1473, 1405, 1292, 1135, 1105, 1032, 810, 787, 730 cm⁻¹ ; MS:298 M!⁺, 185, 141.

EXAMPLE 115

2-(2',3'-Difluorophenyl)-5-n-nonyl-1,3-dioxane

Quantities: compound from Example 10 (31.4 g, 0.155 mol),2,3-difluorobenzaldehyde (21.5 g, 0.15 mol) and 4-toluenesulphonic acid(100 mg). The experimental procedure was as described in Example 114.

Yield=26.9 g (55%); m.p.=27.5°-28.5° C.; ¹ H NMR (CDCl₃): δ0.89 (3H, t),1.10 (2H, q), 1.28 (14H, m), 2.15 (1H, m), 3.56 (2H, t), 4.26 (2H, q),5.71 (1H, s), 7.11 (2H, m), 7.38 (1H, m); IR: 2948, 2920, 2844, 1630,1600, 1486, 1464, 1394, 1385, 1282, 1205, 1145, 1125, 1039, 1023, 834cm⁻¹ ; MS: 326 M!⁺, 212, 140.

EXAMPLE 116

2,3-Difluoro-4-(5'-n-heptyl-1',3'-dioxan-2'-yl) phenylboronic acid(Formula 22)

Quantities: compound from Example 114 (9.0 g, 30 mmol), n-butyllithium(3 cm³, 10.0M in hexanes, 30 mmol) and triisopropyl borate (11.4 g, 60mmol). The experimental procedure was as described in Example 36.

Yield=10.3 g (100%); ¹ H NMR (CDCl₃): δ0.89 (3H, m), 1.11 (2H, q), 1.28(10H, m), 2.12 (1H, m), 3.58 (2H, t), 4.21 (2H, q), 5.68 (1H, s), 7.58(2H, m), 10.33 (2H, s); IR: 3700-3000, 2946, 2916, 2846, 2256, 1675,1448, 1340, 1312, 1260, 1217, 1188, 1150, 1127, 980, 808 cm⁻¹ ; MS: 324M-H₂ O!⁺, 206.

EXAMPLE 117

2,3-Difluoro-4-(5'-n-nonyl-1',3'-dioxan-2'-yl) phenylboronic acid

Quantities: compound from Example 115 (8.6 g, 26 mmol), n-butyllithium(2.6 cm³, 10.0M in hexanes, 26 mmol) and triisopropyl borate (9.8 g, 52mmol). The experimental procedure was as described in Example 36.

Yield=9.6 g (100 %): ¹ H NMR (CDCl₃): δ0.88 (3H, t), 1.10 (2H, q), 1.28(12H, m), 2.14 (1H, m), 3.56 (2H, t), 4.20 (2H, sex), 5.70 (1H, s), 7.35(1H, m), 7.55 (1H, m), 10.35 (2H, s); IR: 3700-3000, 2962, 2932, 2860,2264, 1680, 1486, 1453, 1388, 1343, 1320, 1295, 1261, 1157, 1034, 970,843, 812 cm⁻¹ ; MS: 353 M-OH!⁺, 213, 195.

EXAMPLE 118

2-(2',3'-Difluoro-4'-heptylphenyl)-5-n-nonyl-1,3-dioxane (Formula 25)

n-Butyllithium (3.4 cm³, 10.0M in hexanes, 34mmol) was added dropwise toa stirred, cooled (-78° C.) solution of compound from Example 115(mixture with isomers) (11.2 g, 34 mmol) in dry THF (100 cm³) under anatmosphere of dry nitrogen. The mixture was maintained under theseconditions (3 h) then a solution of 1-iodoheptane (7.7 g, 34 mmol) indry THF (20 cm³) was added dropwise at -78° C. The temperature of thereaction mixture was allowed to reach room temperature overnight. Afterseparation, the aqueous layer was extracted with diethyl ether (2×150cm³), the combined ethereal layers washed with water (2×150 cm³) anddried (MgSO₄). The solvent was removed in vacuo to give the product as abrown oil which was purified by distillation under reduced pressure andrecrystallised several times from methanol to remove the cis-isomer.

Yield=2.5 g (17%); b.p.=94°-98° C./ 1.0 mm Hg; m.p.=40.4° C.; Purity(HPLC): 96.91%; ¹ H NMR (CDCl₃): δ0.88 (6H, sex), 1.09 (2H, q), 1.27(22H, m), 1.57 (2H, q), 2.14 (1H, m), 2.64 (2H, t), 3.55 (2H, t), 4.22(2H, q), 5.69 (1H, s), 6.94 (1H, m), 7.27 (1H, m); IR: 2964, 2928, 2860,1644, 1471, 1401, 1387, 1292, 1162, 1145, 1131, 1091, 1022, 971, 835,813 cm⁻¹ ; MS: 424 M!⁺, 325, 241.

EXAMPLE 119

4-n-Heptoxybenzaldehyde

Anhydrous potassium carbonate (55.5 g, 0.4 mol) was added to a stirredsolution of 4-hydroxybenzaldehyde (24.5 g, 0.2 mol) in acetone (300cm³), over a period of 30 min at room temperature. 1-Bromoheptane (40.3g, 0.225 mol) was added dropwise and the resulting mixture heated underreflux (12 h). The solution was poured into water (1000 cm³), theproduct extracted into diethyl ether (2×300 cm³), and the combinedethereal extracts dried (MgSO₄). The solvent was removed in vacuo andthe product isolated as a colourless oil by distillation under reducedpressure.

Yield=31 g (70%); b.p.=139°-141° C./1.2 mm Hg; ¹ H NMR (CDCl₃): δ0.90(3H, t), 1.30 (6H, m), 1.45 (2H, q), 4.05 (2H, t), 7.00 (2H, m), 7.85(2H, m), 9.90 (1H, s); IR: 2935, 2860, 2805, 2740, 1695, 1580, 1513,1472, 1315, 1260, 1218, 1162, 835 cm⁻¹ ; MS: 220 M!⁺, 121.

EXAMPLE 120

1-Bromo-4-heptoxybenzene

Quantities: anhydrous potassium carbonate (34.8 g, 0.25 mol),1-bromoheptane (19.6 g, 0.11 mol) and 4-bromophenol (17.3 g, 0.1 mol).The experimental procedure was as described in Example 119.

Yield=25.5 g (94%); b.p.=130°-134° C./0.2 mm Hg; ¹ H NMR (CDCl₃): δ0.90(3H, t), 1.33 (6H, m), 1.45 (2H, q), 1.77 (2H, q), 3.91 (2H, t), 6.78(2H, m), 7.38 (2H, m); IR: 2934, 2864, 1490, 1470, 1296, 1246, 1174,1076, 1006, 824, 647,512 cm⁻¹ ; MS: 272 M!⁺, 270 M!⁺, 174, 172.

EXAMPLE 121

1-Iodo-4-octoxybenzene

Quantities: anhydrous potassium carbonate (30 g, 0.22 mol),1-bromooctane (11.7 g, 0.06 mol) and 4-iodophenol (11.0 g, 0.05 mol).The experimental procedure was as described in Example 119.

Yield=16.3 g (98%); b.p.=138°-148° C./0.1 mm Hg; ¹ H NMR (CDCl₃): δ0.89(3H, t), 1.30 (8H, m), 1.43 (2H, q), 1.77 (2H, q), 3.90 (2H, t), 6.68(2H, m), 7.55 (2H, m); IR: 2928, 2860, 1590, 1573, 1489, 1470, 1302,1286, 1246, 1176, 1062, 1030, 1002, 822, 510 cm⁻¹ ; MS: 332 M!⁺, 220.

EXAMPLE 122

1-Bromo-4-nonoxybenzene

Quantities: anhydrous potassium carbonate (60 g, 0.43 mol),1-bromononane (45.3 g, 0.22 mol) and 4-bromophenol (34.6 g, 0.2 mol).The experimental procedure was as described in Example 119.

Yield=57.9 g (97%); b.p.=117°-123° C./0.08 mm Hg; ¹ H NMR (CDCl₃): δ0.90(3H, t), 1.30 (10H, m), 1.45 (2H, q), 1.77 (2H, q), 3.93 (2H, t), 6.78(2H, m), 7.37 (2H, m); IR: 2940, 2868, 1593, 1581, 1494, 1472, 1290,1250, 1174, 1075, 1005, 825 cm⁻¹ ; MS: 300 M!⁺, 298 M!⁺, 174, 172.

EXAMPLE 123

2-(4"-Heptoxy-2',3'-difluorobiphenyl-4'-yl)-5-n-heptyl-1,3-dioxane(Formula 24)

Quantities: tetrakis(triphenylphosphine)palladium(0) (173 mg, 0.15mmol), compound from Example 116 (1.75 g, 5.12 mmol) and compound fromExample 120 (1.36 g, 5 mmol). The experimental procedure was asdescribed in Example 48.

Yield=0.3 g (12%); Purity (HPLC): 99.87%; Mesomorphism (T/°C.): K 77.2N125.2 Iso; ¹ H NMR (CDCl₃): δ0.90 (6H, m), 1.11 (2H, q), 1.28 (16H, m),1.47 (2H, m), 1.82 (2H, q), 2.16 (1H, m), 3.58 (2H, t), 4.00 (2H, t),4.24 (2H, q), 5.73 (1H, s), 6.96 (2H, sex), 7.19 (1H, m), 7.39 (1H, m),7.45 (2H, m); IR: 2954, 2920, 2851, 1612, 1526, 1495, 1467, 1384, 1249,1241, 1182, 1129, 1103, 1026, 826, 810 cm⁻¹ ; MS: 488 M!⁺, 382, 234,214.

EXAMPLE 124

2-(4"-Octoxy-2',3'-difluorobiphenyl-4'-yl)-5-n-heptyl-1,3-dioxane

Quantities: tetrakis(triphenylphosphine )palladium(0) (173 mg, 0.15 mmol), compound from Example 116 (1.75 g, 5.12 mmol) and compound fromExample 121 (1.66 g, 5 mmol). The experimental procedure was asdescribed in Example 48.

Yield=0.65 g (26%); Purity (HPLC): 99.53%; Mesomorphism (T/°C.): K 84.4N124.6 Iso: ¹ H NMR (CDCl₃): δ0.89 (6H, t), 1.11 (2H, q), 1.28 (18H, m),1.47 (2H, m), 1.81 (2H, q), 2.16 (1H, m), 3.58 (2H, t), 4.00 (2H, t),4.24 (2H, q), 5.73 (1H, s), 6.97 (2H, m), 7.19 (1H, m), 7.39 (1H, m),7.43 (2H, m); IR: 2954, 2920, 2852, 1611, 1526, 1494, 1467, 1383, 1244,1181, 1128, 1103, 1024, 824, 808 cm⁻¹ ; MS: 502 M!⁺, 390, 374, 346, 234.

EXAMPLE 125

2-(4"-Nonoxy-2',3'-difluorobiphenyl-4'-yl)-5-n-heptyl-1,3-dioxane

Quantities: tetrakis(triphenylphosphine)palladium(0) (173 mg, 0.15mmol), compound from Example 116 (1.75 g, 5.12 mmol) and compound fromExample 122 (1.36 g, 5 mmol). The experimental procedure was asdescribed in Example 63.

Yield=0.6 g (23%); Purity (HPLC): 99.20%; Mesomorphism (T/°C.): K 86.2N120.4 Iso; ¹ H NMR (CDCl₃): δ0.89 (6H, q), 1.11 (2H, q), 1.29 (20H, m),1.47 (2H, m), 1.81 (2H, q), 2.16 (1H, m), 3.58 (2H, t), 4.00 (2H, t),4.24 (2H, q), 5.74 (1H, s), 6.96 (1H, sex), 7.19 (1H, m), 7.39 (1H, m),7.45 (2H, m); IR: 2962, 2928, 2858, 1612, 1528, 1497, 1471, 1388, 1245,1184, 1131, 1107, 1029, 830, 814 cm⁻¹ ; MS: 516 M!⁺, 389, 361, 234.

EXAMPLE 126

2,3-Difluoro-4-(5-nonyl-1,3-dioxan-2-yl) phenol (Formula 26)

Hydrogen peroxide (10 %, 9 cm³, 26 mmol) was added dropwise to a stirredmixture of compound from Example 117 (1.6 g, 4.5 mmol) in diethyl ether(20 cm³) and aqueous sodium carbonate (5 cm³, 2M) and heated underreflux. The stirred mixture was heated under reflux for a further 2.5 hthen cooled. The ethereal layer was separated and the aqueous layer wasextracted with diethyl ether (2×200 cm³). The combined ethereal layerswere dried (MgSO₄). The solvent was removed in vacuo and the product waspurified by flash column chromatography (dichloromethane).

Yield=0;5 g (32.4 %); m.p.=63°-65° C.; ¹ H NMR (CDCl₃): δ0.91 (3H, t),1.10 (2H, q), 1.30 (14H, m), 2.13 (1H, m), 3.55 (2H, t), 4.22 (2H, q),5.24 (1H, band), 5.62 (1H, s), 6.83 (1H, m), 7.27 (1H, m); IR:3700-3300, 2952, 2920, 2850, 1640, 1522, 1489, 1464, 1389, 1316, 1126,1090, 1025, 973, 830, 810 cm⁻¹ ; MS: 342 M!⁺, 288, 203.

EXAMPLE 127

2-(2,3-Difluoro-4-heptoxyphenyl)-5-nonyl-1,3-dioxane (Formula 27)

Quantities: 1-bromoheptane (0.31 g, 1.46 mmol), potassium carbonate (0.4g, 3 mmol) and compound from Example 126 (0.Sg, 1.46 mmol). Theexperimental procedure was as described in Example 38.

Yield=0.25 g (39 %); Purity (HPLC): 97.95 %; Mesomorphism (T/°C.): K 47(SmA 7) Iso; ¹ H NMR (CDCl₃): δ0.89 (6H, t), 1.09(2H, q), 1.27 (22H, m),1.80 (2H, qn), 2.12 (1H, m), 3.54 (2H, t), 4.03 (2H, t), 4.21 (2H,),5.63 (1H, s), 6.73 (1H, m), 7.27 (1H, m); IR: 2964, 2920, 2858, 1630,1515, 1484, 1463, 1394, 1317, 1292, 1130, 1090, 1021, 803 cm⁻¹ ; MS: 440M!⁺, 341, 325, 256, 159.

EXAMPLE 128

2-(2,3-Difluorobiphenyl-4'-yl)-5-octyl-1,3-dioxane (Formula 29)

Quantities: compound from Example 14 (10.7 g, 30 mmol), compound fromExample 36 (5.5 g, 35 mmol), tetrakis(triphenylphosphine)palladium(0)(1.04 mg, 0.9 mmol) and aqueous sodium carbonate (30 cm³, 2M). Theexperimental procedure was as described in Example 63.

Yield=10.8 g (92.7 %); Purity (HPLC): 98.63 %; Mesomorphism (T/°C.): K52.2 SmA 77.0 Iso; ¹ H NMR (CDCl₃): δ0.89 (3H, t), 1.11 (2H, q), 1.28(12H, m), 2.15 (1H, m), 3.56 (2H, t), 4.26 (2H, q), 5.48 (1H, s), 7.14(3H, m), 7.56 (4H, m); IR: 2962, 2932, 2858, 1626, 1593, 1573, 1483,1408, 1386, 1261, 1127, 1083, 1028, 1020, 897, 812, 786 cm⁻¹ ; MS: 388M!⁺, 275, 217.

EXAMPLE 129

2-(2,3-Difluorobiphenyl-4-yl)-5-nonyl-1,3-dioxane

Quantities: compound from Example 15 (7.4 g, 20 mmol), compound fromExample 36 (3.5 g, 22 mmol), tetrakis(triphenylphosphine)palladium(0)(1.16 mg, 1 mmol) and aqueous sodium carbonate (20 cm³, 2M). Theexperimental procedure was as described in Example 48.

Yield=6.5 g (73.4 %); Purity (HPLC): 97.57 %; Mesomorphism (T/°C.): K74.0 SmA 75.1 Iso; ¹ H NMR (CDCl₃): δ0.89 (3H, t), 1.28 (16H, m), 2.15(1H, m), 3.56 (2H, t), 4.26 (2H, q), 5.47 (1H, s), 7.15 (3H, m), 7.44(4H, m); IR: 2940, 2868, 1600, 1580, 1490, 1480, 1393, 1272, 1135, 1090,1032, 903, 833, 788 cm⁻¹ ; MS: 402 M!⁺, 289, 217.

EXAMPLE 130

2,3-Difluoro-4'-(5-nonyl-1,3-dioxan-2-yl)biphenylboronic acid

Quantities: compound from Example 129 (6 g, 15 mmol), n-butyllithium (10cm³, 1.55M in hexanes, 15.5 mmol) and triisopropyl borate (5.7 g, 30mmol). The experimental procedure was as described in Example 28.

Yield=6.7 g (99.4 %); Mesomorphism (T/°C.): K 88.0N 180.0 Iso; ¹ H NMR(CDCl₃): δ0.89 (3H, t), 1.11 (2H, q), 1.27 (14H, m), 2.14 (1H, m), 3.55(2H, t), 4.23 (2H, m), 5.47 (1H, s), 7.13 (1H, m), 7.45 (1H, m), 7.55(4H, m); IR: 3700-3200, 2972, 2940, 2868, 1636, 1490, 1478, 1459, 1350,1324, 1267, 1177, 1030, 821 cm⁻¹ ; MS: 612, 611, 542, 445 M-1!⁺, 428,206.

EXAMPLE 131

2,3-Difluoro-4'-(5-nonyl-1,3-dioxan-2-yl)biphenyl-4-ol (Formula 30)

Quantities: hydrogen peroxide (10 %, 10 cm³, 29 mmol), aqueous sodiumcarbonate (5 cm³, 2M) and compound from Example 130 (1.6 g, 3.6 mmol).The experimental procedure was as described in Example 126.

Yield=1 g (66.4 %); Mesomorphism (T/°C.): K 115 (N 88.7) Iso; ¹ H NMR(CDCl₃): δ0.90 (3H, t), 1.12 (2H, q), 1.30 (14H, m), 2.15 (1H, m), 3.56(2H, t), 4.26 (2H, q), 5.20 (1H, d), 5.47 (1H, s), 6.84 (1H, m), 7.07(1H, m), 7.52 (4H, m); IR: 3600-3100, 2960, 2924, 2852, 1626, 1609,1507, 1467, 1418, 1386, 1325, 1077, 1021, 840, 807 cm⁻¹ ; MS: 418 M!⁺,289, 233.

EXAMPLE 132

(S,S)-2,3-Difluoro-4'-(5-nonyl-1,3-dioxan-2-yl)biphenyl2-fluoro-3-methylpentate (Formula 31)

Quantities: compound from Example 131 (0.8 g, 2 mmol),(S,S)-2-fluoro-3-methylpentoic acid (0.27 g, 2 mmol),N,N'-dicyclohexylcarbodiimide (0.41 g, 2 mmol), 4-(N,N-dimethylamino)pyridine (0.03 g, 0.2 mmol). The experimental procedurewas described in Example 108 except for using dichloromethane instead ofTHF and diethyl ether.

Yield 0.4 g (37 %); Purity (HPLC): 97.17%; a!_(D) ²⁵ =0°; Ps=222 nCcm⁻²(73.9° C.); Mesomorphism: (T/°C.) K 93.5 SmC 112.6 SmA 125.1 Iso; ¹ HNMR (CDCl₃): δ60.89 (3H, t), 1.01 (2H, t), 1.11 (2H, q), 1.15 (3H, t),1.27 (14H, m), 1.57 (1H, 2×m), 2.15 (1H, m), 2.23 (1H, m), 3.56 (2H, t),4.26 (2H, q), 5.08 (1H, q), 5.47 (1H, s), 7.01 (2H, M), 7.20 (1H, m),7.56 (4H, m); IR: 2962, 2926, 2854, 1790, 1765, 1593, 1570, 1385, 1262,1228, 1168, 1127, 1113, 1023, 1012, 825 cm⁻¹ ; MS: 534 M!⁺, 417, 351,234.

EXAMPLE 133

2,3-Difluoro-4- 4-(5-octyl-1,3-dioxan-2-yl)phenyl! benzoic acid (Formula32)

Quantities: compound from Example 128 (5.6 g, 15.4 mmol), n-butyllithium(1.5 cm³, 10.0M in hexanes, 15 mmol). The experimental procedure was asdescribed in Example 104.

Yield=5.2 g (83.5 %); Mesomorphism (T/°C.): K 177.5N 220.9 Iso; ₁ H NMR(CDCl₃): δ0.89 (3H, t), 1.11 (2H, q), 1.28 (10H, m), 2.14 (1H, m), 3.57(2H, t), 4.25 (2H, q), 5.48 (1H, s), 7.23 (1H, m), 7.58 (4H, m), 7.77(1H, m); IR: 3700-2400, 2966, 2932, 2860, 1702, 1624, 1467, 1422, 1384,1306, 1128, 1082, 1026, 820, 781 cm⁻¹ ; MS: 432 M!⁺, 261, 234.

EXAMPLE 134

(+)-2-Fluorooctyl 2,3-Difluoro-4- 4-(5-octyl-1,3-dioxan-2-yl)phenyl!benzoate (Formula 33)

Quantities: compound from Example 133 (1.7 g, 4 mmol), 2-fluorooctanol(0.6 cm³, 4 mmol), N,N'-dicyclophexylcarbodiimide (0.83 g, 4 mmol),4-(N,N'-dimethylamino)pyridine (0.05 g, 0.4 mmol). The experimentalprocedure was described in Example 108 except for using dichloromethaneinstead of THF and diehtyl ether.

Yield=0.6 g (26.7 % ); Purity (HPLC): 99.21%; a!_(D) ²³ =+7.7°;Mesomorphism: (T/°C.) K 87.0 SmA 116.5 Iso; ¹ H NMR (CDCl₃): 0.90 (6H,m), 1.12 (2H, q), 1.30 (20H, m), 1.78 (2H, m), 2.15 (1H, m), 3.56 (2H,t), 4.26 (2H, q), 4.32-4.60 (2H, m), 5.48 (1H, s), 7.25 (1H, m), 7.59(4H, m), 7.77 (1H, m); IR: 2956, 2922, 2852, 1705 1627, 1468, 1452,1398, 1386, 1322, 1305, 1233, 1222, 1165, 1132, 1083, 1025, 820, 777cm⁻¹ ; MS: 562 M!⁺, 415, 387, 275.

EXAMPLE 135

(+)-2-Octyl 2,3-Difluoro-4- 4-(5-octyl-1,3-dioxan-2-yl)phenyl! benzoate

Quantities: compound from Example 133 (1.7 g, 4 mmol), 2-octanol (0.5cm³, 4 mmol), N,N'- dicyclophexylcarbodiimide (0.83 g, 4 mmol),4-(N,N'-dimethylamino)pyridine (0.05 g, 0.4 mmol). The experimentalprocedure was described in Example 134.

Yield=0.3 g (13.8 % ); Purity (HPLC): 99.40%; a!_(D) ²¹.5 =+24.3°;Mesomorphism: (T/°C.) K 50.5 SmA 83.8 Iso; ¹ H NMR (CDCl₃): δ0.89 (6H,m), 1.11 (2H, q), 1.28 (20H, m), 1.36 (3H, d), 1.59-1.80 (2H, m), 2.15(1H, m), 3.57 (2H, t), 4.26 (2H, q), 5.19 (1H, sex), 5.48 (1H, s), 7.23(1H, m), 7.58 (4H, m), 7.72 (1H, m); IR: 2958, 2924, 2854, 1705, 1623,1458, 1384, 1303, 1284, 1220, 1150, 1126, 1083, 1026, 823, 779 cm⁻¹ ;MS: 544 M!⁺, 519.

What we claim is:
 1. A ferroelectric liquid crystal compound of the formula A: ##STR13## Wherein X is CH or B R¹, R², are each A¹, OA¹, OCOA², or COOA² A¹ is a straight or branched chain alkyl group containing from 5 to 10 carbon atoms and may be substituted with one or more F or CN; A² is a straight or optically active branched chain alkyl group containing from 5 to 10 carbon atoms and may be substituted with one or more F or CN and if straight may be unsubstituted; Y² may be (CH₂)_(p), (CH₂)_(p) COO or OCO(CH₂)_(p) ; p is from 0 to 10; m is 1, or, if X is CH and Y⁴ is a covalent bond, may be 0, provided that if m is 1, then p is not 0; only one of Z₁ and Z₂ are F and, when not F, are H; Y³ is a covalent bond; Y⁴ is a covalent bond or, ##STR14##
 2. A compound according to claim 1 wherein A² is an optically active branched chain alkyl group containing form 5 to 10 carbon atoms and substituted by a single F or CN.
 3. A compound according to claim 1, wherein R² is OA¹.
 4. A compound according to claim 1, wherein R² is OCOA².
 5. A compound according to claim 1, wherein R² is COOA².
 6. A compound according to claim 1 wherein X is B; Y² is (CH₂)_(p) wherein p is 0; m is 1; Z₁ is F; and Z₂ is H.
 7. A compound according to claim 1 wherein X is CH; p is 0; m is 0 and Y⁴ is a covalent bond.
 8. Compositions comprising one or more compounds according to claim 1 as components in cells of LCD devices.
 9. Composition according to claim 8, and having a Smetic C phase range of from -20° C. to 93° C.
 10. Liquid crystal cells and liquid crystal devices comprising said cells containing a composition according to claim
 8. 11. (2",3"-difluoro-4"-n-nonoxy-4'-biphenylyl)-4-n-nonyl-2,6-diox aborinane. 